TW572906B - Fluorine-containing material for optical waveguide - Google Patents

Description

572906 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a fluorine-containing optical waveguide for the hardened product in a fluorine-containing prepolymer. The resulting material for the fluorinated optical waveguide and the hardened material are used in the core portion or the cladding portion and the material is used. "I Xin Zhuo Qiong's Pilot Wave Path Model [Background Technology]: Towards the height of the optical communication system m development: Among them, the optical waveguide system is as follows: Gao Gai: General 'as a pilot wave path material, the system requirements ^ Zuomu. -The controllability of the transparency in the near-infrared wavelength region, etc. f ..., plutonium, and water and humidity resistance Now, as a material of the optical waveguide # 1 300 to 1 550nm in the near-infrared region J: Low light loss with Shigongzai. However, problems such as the difficulty of changing the manufacturing process system and the occurrence of such problems occur, and it is not easy to obtain. Goods and good generality. On the other hand, due to the use of polymer by spin coating method, etc .: / leather road, the system can be used to simplify the process, can also become a large area ;: Because of &, manufacturing olefin, acrylic resin or polyimide, etc., in the polybenzyl material, as far as the aforementioned near-infrared region is concerned, the fat material is large (poor transparency $ 6 pages2066-4683-PF ( N); Tcshiau.ptd 572906 Fifth invention description (2)), therefore, the light loss becomes large, and the incompatible hydrogen is replaced with deuterium (D) or fluorine (^. These resins are also used to improve the optical properties. I am trying to improve the loss. The optical characteristics are significantly reduced. That is, the absorption of the linear region caused by water absorption over time makes the transmission loss worse, and increases the near infrared as a transparent low water absorption in the near infrared region. High-molecular-weight polymer materials are proposed to have a relatively low loss and non-crystalline fluorine-containing polymerization. ((* Patent Laid-Open: Japanese Patent Laid-Open No. 2000-81 51 of the f-type structure), etc. ^ ❶ ―1 No. 90202, these non-concluded The problem is that the fluorinated polymer has a problem, but the glass transition temperature is low. However, there is no problem. The polymer itself becomes rough, and cracks occur at the glass transition temperature. In addition, in the perfluorinated formation process, there is a compound whose range of refractive index can be controlled = of: M; crystalline fluorine-containing polyleaf core-clad waveguide, there is a considerable amount of this in use In the state where the core portion of the waveguide is set, the system exists. For example, it is used as an appropriate cladding material. Therefore, as shown in the relationship, it cannot be shown in the bulletin. 〇 " 1519 compound. In the state of this material, ":; :::: the rate of the environment must be re-dispersed, the rate = non-uniform shot, so it has the so-called large-scale trade-off Disadvantages. Like this, regarding the material of the optical waveguide ^ shell 2 — the cause of the problem, because Λ, I hope to solve it. :: Method to solve the new k 2 question 4 optical waveguide

2066-4683-PF (N); Tcshiau.ptd Page 7 ^ / 2906

V. Description of the invention (3) Road materials. [Disclosure of the invention] For the purpose of the present invention, it is possible to use a specific material containing fluorine and a kind of material for fluorine-containing optical waveguides (hereinafter referred to as "injection, prepolymer, and maintain transparency in the near-infrared region." "In the light-guiding wave path: 2: transparency"), at the same time, "the purpose of the invention can be achieved by the flexibility of the local elasticity and financial heat. Line transparency, at the same time: Don't = a material that can maintain the near-infrared film process ... It is a process that can be performed by light: formula, method, etc., and can also be made into a large surface light guide. The area of the wave path can be reduced to produce a light guide with reduced water absorption. In addition, the purpose of the present invention is to provide a light guide wave path ## system for the use of these materials to produce klTb ze wave path members and light guide wave path type clothing. In order to achieve this result, we found that the non-surname σ chain ends characterized by carbon-carbon double bonds at the side of the polymer are characterized by ^ ^ ^ ^ a, ^ ^ ^ τ T beer low near-infrared 硬化 hardened product with high transparency and heat resistance. It is near-monthly and hard-wearing. In addition, it has been found that a hardened film of carbon-prepolymer at the end of the side chain is conducive to being a special 疋 3 gas. Thermal light guide material. It has near-infrared transparency and resistance to the invention. According to the intention i ', the inventors have completed the following

2066-4683-PF (N); Tcshiau.ptd Page 8 572906 V. Description of the invention (4) The first aspect of the present invention relates to a fluorine-containing optical waveguide material, which is composed of a fluorine content of 25% by weight or more. It is a non-crystalline polymer and is a fluorine-containing prepolymer (I) having a carbon-carbon double bond in a polymer side chain and / or a polymer main chain terminal. The fluorine-containing prepolymer (I) used in the present invention is preferably a chemical formula (1): — ~~… — (1) [In the chemical formula, the structural unit M is a chemical formula (M): —- (- CX ^ 2—CX3 *) — I (Μ) (CX4X5h (-C = 〇) b (〇> T-Rf (In the chemical formula, X1 and X2 are the same or different to become Η or f; χ3 system η, F, CH3 or CF3; X4 and X5 are the same or different to form η, F or cf3; Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing fluorine having a bond having 2 to 100 carbon atoms Burning the base and combining 1 to 3 of Υ1 (γι is an organic group having an ethylenic carbon-breaking double bond at the end and a monovalent organic group having 2 to 10 carbon atoms); ^ is an integer of 0 to 3; b and c It is the same or different and becomes 0 or 1) The structural unit due to fluorinated ethylene and monomer, structural unit A is caused by the fluorinated ethylenic monomer and copolymerizable monomer given to the structural unit M Structural Units] As shown in the figure, the number of structural units containing ο · ι ~ 100 mol% and the number of structural units A of 0 ~ 99 mol% with an average molecular weight of 500,000 ~ 10,000 Fluoropolymer 0 The fluorinated prepolymer (I) system More preferably, it is a fluorine-containing prepolymer having a maximum absorbance coefficient in a wavelength range of 129 to 132 ° and / or a wavelength range of 1 530 to 1 570 nm of 1 cur1 or less.

572906

The second type of the present invention relates to a component for a fluorine-containing optical waveguide, which is composed of a hardened product containing a random prepolymer (z), or in addition to a fluorine-containing prepolymer (1). Materials (containing photo-radical generators (π — 1) or photo-acid generators (u — 2) and other active energy ray hardening initiators ^ π)) hardened by light curing, and the composition contains The maximum value of the absorbance coefficient in the wavelength range of 1 290 to 1 320 nm and / or the wavelength range of 1530 to 1570 nm of these hardened members is 1 cm-i or less. The third aspect of the present invention relates to an optical waveguide type element, and the aforementioned second type of the fluorine-containing optical waveguide component according to the present invention is used in a core portion and / or a cladding portion. [Best Embodiment of the Invention] As a suitable polymer of the fluorine-containing prepolymer (I) used in the present invention, as described above, the chemical formula (1): — ~ — (1) [In the chemical formula, Structural unit M is chemical formula (Μ): —fcx'x2—cx3 ^ — I (Μ) (CX4X5h ~~ ^ rC = 0) b (0 ^ ~ R f (In the chemical formula, X1 and X2 are the same or different It becomes H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different to form Η, F or CF3; Rf is a sintered group containing 1 to 40 carbon atoms or has 2 to 3 carbon atoms 100% mysterious bond of fluorinated alkyl group and an organic group of 1 to 3 Y1 (Y1 is an ethylenic carbon-carbon double bond at the end and a monovalent organic group having 2 to 10 carbon atoms); a series 〇 ~ 3 of the whole

2066-4683-PF (N); Tcshiau.ptd Page 10 572906

V. Description of the invention (6) Numbers; b and c are the same or different and become 0 or 1) The structural unit caused by the gas-containing ethylenic monomer shown in the figure), the structural unit A is due to the beer to the structural unit M Structural units caused by fluorinated ethylenic monomers and copolymerizable monomers], including 0.1 to i 00 mole% of the structural unit M and 0 to 99.9 mole% of the structural unit A Fluoropolymers having a number average molecular weight of 500 to 丨 οοοοοο. In other words, it becomes a homopolymer having a structural unit M caused by a fluorine-containing ethylenic monomer having a carbon double bond in the side chain of the polymer, which can be hardened due to the reaction, or The structural unit μ is a copolymer of essential components. In the Rf of the structural unit M, at least one line of γι is preferably bound to the Rf ^ terminal. The structural unit M in the fluorine-containing prepolymer (I) used in the present invention is also preferably the chemical formula (M1): — »(rCXlX2—CXz ^ — I (Ml) (CX4X5V-fO) ^ — R f (In the chemical formula, X1 and X2 are the same or different to become H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different to become Η, F or CF3; Rf is at the fraction 1 Fluorine group of ~ 40 or fluorinated alkyl group having an ether bond of 2 to 100 carbon atoms, and 1 to 3 Y1 (Y1 has an ethylenic carbon-carbon double bond at the end and a carbon number of 2 ~ 10 is a monovalent organic group) organic group; a is an integer of 0 ~ 3; c is 0 or 1) The structural unit M1 caused by the fluorinated ethylenic monomer is included. Fluorine prepolymer, especially near infrared

2066-4683-PF (N); Tcshiau.ptd Page 11 572906 V. Description of the invention (7) Transparency 咼 'is not limited to homopolymers in the structural unit 乂 丨, even if it is copolymerized by increasing the composition of the structural unit M1 It is also desirable to improve the transparency of the near red line. In addition, a more specific example of the structural unit M1 is more ideal, and the formula (M2): "Zon-fCH2-CF-)-I (M2) CF 2-〇-R f (In the chemical formula, the Rf system 1 to 3 carbon atoms are bonded to a fluoroalkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having an ether bond to 2 to 100 carbon atoms (γι has an ethylenic carbon-carbon double bond at the end Bonded and monovalent organic group with carbon number of 2 to 10) The structural unit M2 shown by the fluorine-containing ethylenic monomer shown in the organic group). The structural unit M2 has an ethylenic carbon-carbon double bond at the end. The structural unit of the fluorine-containing allyl bond of the bond can not only improve the near-infrared transparency, but also has good polymerizability. In particular, it has good homopolymerization and copolymerizability with other fluorine-containing vinyl monomers. Therefore, it is quite desirable. In addition, other ideal specific examples of the structural unit M1 are the chemical formula (M3): Yu Er— (rCF2—CF ^ — (M3)

I 〇-R f (In the chemical formula, Rf is a fluorinated alkyl group having 1 to 40 carbon atoms or a fluorinated alkyl group having an ether bond with 2 to 100 carbon atoms and combines 1 to 3 of fluorene 1 ( γι is a structural unit M3 due to a fluorine-containing ethylenic monomer as shown in an organic group) having an ethylenic carbon-carbon double bond at the end and a monovalent organic group of 2 to 10 carbon atoms). The structural unit M3 is a fluorine-containing ethyl having an ethylenic carbon-carbon double bond at the end.

2066-4683-PF (N); Tcshiau.ptd Page 12 572906

The structural unit of W can improve the near-infrared transparency. Since the copolymerizability between vinyl monomers is good, it is quite desirable. The fluorine-containing prepolymer of the chemical formula (1) used in the present invention (, 'γ included in the structural units M, M1, M2, and M3, as described above)' has an ethylenic carbon-carbon double bond at the end And the carbon number of 2 to 10 months, J-based. Valence organic The carbon-carbon double bond system in Y1 has At i, which can cause polycondensation reaction, etc., and can give a hardened (crosslinked) body. In detail, it can be added, for example, by contacting radicals or cations to facilitate the addition of 2 hardening (cross-linking) between the fluorine-containing prepolymer (I) and the fluorine-containing prepolymer (I). ()), Cause polymerization or condensation reaction, and / ^, 卞 hardened (parent). As the first type of ideal γι, it is ~ ^ 〇V-4C = 〇) e —Υ2 (In the chemical formula, Y2 is an alkenyl group having 2 to 5 carbon atoms having an ethylenic carbon-carbon double bond at the terminal or Fluorinated alkenyl groups; d or e are the same or different and become 0 or as ideal Y2, preferably CX6 = CX7X8 (in the chemical formula 'X6 system Η, F, CH3 or CF3; X7 and X8 systems are the same Or different to become Η or F), the Υ2 group is caused by the contact of free radicals or cations to make the hardening reactivity 0. As a specific example of the ideal Υ2, a series of examples

2066-4683-PF (N); Tcshiau.ptd Page 13 572906

ch3

I

-CH = CH2, -CF = CH2, -C = CH2, --CF = CF cf3

I

One C = CH2, one CH = CHF, etc. In addition, as a more ideal Y1, a series of 10 (C = 0) cx6 CX X (in the chemical formula, χ6 is Η, F, c or 化; χ7 and 乂 8 are the same or different and become Η or F) In particular, the wealth-based system makes the hardening reactivity even higher through the contact of free radicals. In this regard, 'those who want the same' and 'can be easily hardened by light hardening, etc .: It is also quite ideal. ^ Fang As a specific example of the aforementioned more ideal γι, the series is ch3

I II 〇 II 〇 10C-CH = CH2, -0C -C = CH2, -0c-CF = CHp,

II 〇 cf3

I 〇c-c = ch2, 〇c — cf = cf2

II II o 〇 etc. As specific examples of other ideal Y1, the series is given as ch = ch2, ch2ch = ch2, 〇ch2ch = ch2, 〇ch = ch2, 〇cf = cf2,

2066-4683-PF (N); Tcshiau.ptd Page 14 572906 V. Description of the invention (ίο)-C-och = ch2,-C-0ch2ch = ch2

II II 〇 〇

X

I

--CH — CH2〇C — C = CH2 (X: H, F, CH3), I II OH 〇 〇 II -ch ~ ch2occx = ch2 (x: h, f, ch3), 〇ccx = ch2

-Chch2〇ch2ch = ch2, -CHCH2OCH2CH = CH2 1 I OH OCH2CH = CH2, etc. Even in Y1, those who have a structure of -〇 (c = 0) CF = CH2 can improve the near-infrared transparency, and the curing (crosslinking) reactivity system is particularly high, and the cured product can be obtained efficiently. On the other hand, it is quite ideal.

In addition, the aforementioned organic group Y1 having a carbon-carbon double bond in a side chain may be introduced to the end of the polymer main chain. ^ In the fluorine-containing prepolymer (I) used in the present invention, Rf is included in one of the structural units M, M1, M2, and M3 — (the base of γ! Is removed by -Rf), and the number is 1 ~ 40 fluorine-containing alkylene group or fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. The Rf_ group may be at the carbon atom contained,

572906 V. Description of the invention (11) Combined with a fluorine atom, the fluorinated alkylene group preferably contains more, and it is more preferably 5% by weight of the total prepolymer (I). The purpose of the near-infrared transmittance coefficient of energy is to maintain it highly, and the fluorine content of the fluorine atom of the fluoroalkyl group is sufficient for clarity, that is, the near-infrared is at an Rf-based carbon number. The solubility of the solvent and the hardness of the fluorine-containing hardened product having an ether bond or the number of carbon atoms of a mechanical gas-containing sulfinyl group are fluoroalkylene groups having an ether bond of 2 to 20. The carbon atom combines a fluorine atom and a hydrogen atom or a chlorogen fluorine-containing alkylene group having an ether bond, but the most (high I content ratio) is more preferable or a perfluoroalkyl group having an ether bond. The fluorine-containing f ratio is 25% by weight or more, preferably as described in April 1J, and the fluorine-containing prepolymer is improved (I especially because the heat resistance of the cured product is improved or the degree of hardening (crosslinking density) is increased, It can also be transparent, and as a result, it becomes quite ideal. When it is too large, the state of the fluoroalkylene group decreases, or the transparency decreases, and the state of the alkylene group decreases the polymer itself or characteristics. , So that it becomes unsatisfactory. It is preferably 1 ~ 2 0, more preferably 1 ~; i 〇. The carbon number is preferably 2 ~ 3 0, and it is more reasonable as a specific example of the ideal of R f — , Series cf3

I, Xing CF2CFMCH2hr, Xing CH2CF2 > ^ CH2 > 7r, CF3

I-(CU2hrC- (above, m: l ~ 10, n: 0 ~ 5),

I CF3

2066-4683-PF (N); Tcshiau.ptd page 16 572906 V. Description of the invention (12) cf3

I ^ CF 2CF 2hr < CF 2CFhr ^ CH2hr > ^ CF2CF2h-iCH2CF2hr < C ^ 2hr ^ CF3 cf3

I I-< CF2hrC-,-< CH2CF2h- ^ CF2CF) 1ir (CH2 > ir,

CF 5) (above, 1: 1 to 10, m: 1 to 10, n 4CFCF2〇MCF2〇MCX102CF2CF2O> T (CX11MCFMCH2) -r X9 X12 or

-fCF2CF〇MCF2O> T < CF2CF2CX102O) 1CF2 (CF) T < CH2V X9 X12 (above, X9, X12 is F or CF3, X1Q, X11 is H or F; o + p + q is 1 to 3 〇; r is 〇 or 1; s, t is 0 or 1) and so on. As mentioned above, the structural unit M constituting the fluorine-containing prepolymer (Ϊ) used in the present invention is preferably the structural unit M1, and as the structural position M1, it is also preferably the structural unit M2 or the structural unit M3. . Therefore, specific examples of the construction unit M2 and the construction unit M3 will be described. ? As an ideal specific example of the monomer constituting the structural unit M2, a series of examples are ch2 = cfcf2〇cf-γι, ch2 = cfcf2〇cfch2--1, I I 2

CF CF.

2066-4683.PF (N); Tcshiau.ptd Page 17 572906 V. Description of the invention (13) ch2 = cfcf2ocfch2o-y \ ch2 = cfcf2o ^ cfcf2o ^ cf- ~ y \

I II cf3 cf3 cf3 CH2 = CFCF20 (CFCF20) -nCFCH2-Y1,

I I cf3 cf3 ch2 = cfcf2〇 (cfcf2〇hcfch2och2chch2-y1,

III cf3 cf3 y1 CH2 = CFCF2O ^ CF2CF2〇h1CF2-Y1, CH2 = CFCF20- (CF2CF20 > -nCF2CH2-Y1, CH2 = CFCF2〇- (CF2CF2CF2〇hCF2CF2 ~ Y1, CH2 = CFCF2CKCF2CF2CF2CF2CFHYCF2CFH -(CH2CF2CF2〇hCH2CF2-Y \ CH2 = CFCF2CXCH2CF2CF2〇hCH2CF2CH2-Y1, CH2 = CFCF20-eCF2CF2 > -nY1, cf3 CH2 = CFCF20 (CF2CF) -nCH2-Y1 (above, n is an integer of 1 to 30; Y1 is an integer Same as above). In more detail, CH2 = CFCF20- (CFCF2〇hCFCH2OCCX = CH2,

I I II cf3 cf3 ο CH2 = CFCF2〇- (CFCF2〇hCFCH2OCH2CHCH2OCCX = CH2,

I I II cf3 cf3 〇 〇ccx = ch2

II 〇 2066-4683-PF (N); Tcshiau.ptd page 18

(I 572906 V. Description of the invention (14) CH2 = CFCF2CKCFCF2〇hCFCH2〇CH = CH2,

I I cf3 cf3 CH2 = CFCF204CFCF20hCFCH20CH2CH0CH = CH2

I I I cf3 cf3 〇ch = ch2 CH2 = CFCF2〇4CFCF2〇hCF = CF2

I cf3 ch2 = cfcf2〇 ^ cfcf2o ^ cfc〇〇ch = ch2

I I cf3 cf3 CH2 = CFCF2CKCFCF2〇HCFCH2OCH2CH = CH2

I I cf3 cf3 CH2 = CFCF2CKCFCF2〇hCFCH2〇CH2CHCH2〇CH2CH = CH2

I I I cf3 cf3 〇ch2ch = ch2 / Rfl ch2 = cfcf2o- (cfcf2o ^ cfc ——〇ccx = ch2 I I \ Rf2 丨 丨 cf3 cf3 Rf 〇 ch2ch = ch2

I

CH2 = CFCF20- < CFCF20hCF ~ C ~ 0CCX = CH2 II II cf3 cf3 〇ch2ch = ch2 (above, Rf1, Rf2 is a perfluoroalkyl group with 1 to 5 carbon atoms; X is H, CH3, F or CF3; n Is an integer from 0 to 30) and so on. As an ideal specific example of the monomer constituting the structural unit M3, a series of CF2 = CF〇CF2CF2 —Y1, cf2 = cfocf2cf2ch2-y1, CF2 = CF〇CF2CF2CH2〇CH2CHCH2 —Y1, I χ mill Υ 2066-4683-PF (N ); Tcshiau.ptd Page 19 572906 V. Description of the invention (15) CF2 = CFCKCF2CF > irY ^ CF2 = CFCKCF2CFO) -nCF2CF2CH2 ~ Y1, CF3 cf3 CF2 = CF〇4CF2CF〇hrCF2CF2CH2OCH2CHCH2-Y1 CF1 Y1 CFY = CFY ^ CF2 = CF〇-fCF2) TCH2-Y1, cf2 = cfocf2cf2ocf2-y1, cf2 = cfocf2cf2ocf2ch2 ~ y \ cf2 = cfocf2cf2〇cf2ch2och2chch2 ~ y1, CF2 = CFOCF2CF2CH2OCF2CF2-CF2-Y1, CF1F2, CF2Y2 The foregoing; n is an integer of 1 to 30) and so on. In more detail, CF2 = CFO (CF2CF〇h7 < CF2hCH2OCCX = CH2,

I II cf3 〇 CF2 = CFO (CF2CFO) 7ir (CF2 ^ CH2OCH2CHCH2OCCX = CH2,

I II cf3 〇 occx = ch2

II 〇 CF2 = CFGKCF2CF〇MCF2 " hCH2〇CH = CH2, CF3 CF2 = CFGKCF2CF〇h ^ CFihCH2〇CH2CH〇CH = CH2

II cf3 〇ch = ch2 CF2 = CFCKCF2CFCMCFjhC〇CH = CH2, cf3 1ΪΒ1 2066-4683-PF (N); Tcshiau.ptd page 20 572906 5. Description of the invention (16) CF2 = CFO ^ CF2CFO > 7 ^ CF ^ -nCH2OCH2CH = CH2,

I cf3 CF2 = CFCKCF2CF〇hr < CF2firCH2OCH2CHCH2OCH2CH = CH2, CF. OCH, CH = CH5

Rf II 〇 CF2 == CFO- (CF2CF〇hr < CF2 > 17C-〇CCX = CH2 CF ·

Rf CH2CH = CH2 CF2 = CF〇- < CF2CFO > ^ CF2) li-C-〇CCX = CH2

I II CF 3 〇ch2ch = ch2 (above, Rf1, Rf2 are perfluoroalkyl groups with 1 to 5 carbon atoms; m is an integer from 0 to 30; η is an integer from 1 to 3; X is Η, CH3, F or CF3) and so on. In addition to these structural units M2 and M3, as an ideal specific example of the monomer constituting the structural unit M of the fluorine-containing prepolymer (I), a series of examples include CF2 = CFCF2—〇—Rf—Y1, CF2 = CFCF2 〇-Rf-CH2CHCH2_Y1, Y1 CF2 = CF-R f-Y1, CF2 = CF-R f-CH2CHCH2-Y1, γΐ CH2 = CH — R f — Y1, CH2 = CH — R f — CH2CHCH2 — Y1

I Y1

2066-4683-PF (N); Tcshiau.ptd Page 21 572906 V. Description of the invention (17) CH2 = CHO ~ R f-CH2CHCH2-Y1 Y1 (above, Y1 and one Rf -Is the same as above). More specifically, CF2 = CFCF2OCF2CF2CF2-Y1, cf2 = cfcf2ocf2cf2cf2ch2-y1, cf2 = cfcf2〇cf2cf-Y1, CF2 = CFCF2〇CF2CFCH2—Υ1, cf3 cf3 cf2 = cfcf2〇cf2cfch2Och1ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2ch2

I CF3 CF2 = CFCF2-Y1, CF2 = CFCF2CH2-Y1, CF2 = CFCF2CH2〇CH2CHCH2 — Y1

I Y1 ch2 = chcf2cf2ch2ch2 ~ y1, ch2 = chcf2cf2-y1, ch2 = chcf2cf2ch2-y1, ch2 = chcf2cf2cf2cf2-y1, CH2 = CHCF2CF2CF2CF2CH2-Y1, ch2 = chcf2cf2cf2cf2ch2och2och2och2och2

I Y1 ch2 = choch2cf2cf2-y1, CH2 = CHOCH2CF2CF2CH2-Y1 (the above and Y1 are the same as above), etc. In the fluorine-containing prepolymer (I) used in the present invention, the structural unit A is an arbitrary component, and it is not particularly limited if the monomer can be copolymerized with the structural unit M, M1, M2, or M3. Cooperation becomes purpose

2066-4683-PF (N); Tcshiau.ptd Page 22 5. Description of the invention (18) The gas prepolymer (work) or its hardened product is selected locally. It can be used as the structural unit A, which can be exemplified (D is composed of a functional group containing a ethylenic ° · γ U & unit.) The structural unit ① is a structural unit that can be highly c hardened. Near-infrared transparency, and the convergence of the polymer, especially the solvent, especially the base material, is quite ideal, in addition, it can also; In this regard, ancient and similar In this regard, the ideal fluorine-containing ethylenic single-system chemical formula (3) having an S 旎 group at the intersection other than Y1 is: the structure of the I body is in the early position ①, — (· ΟΧηχ12—cx13 ^ — (cxi42-h —E〇> r-Rf4-z (3) (in the chemical formula, χη, P, and ^ 3 are the same or different and become H nails; X14 is Η, F, CF3; h is an integer from 0 to 2; i is 0 or !; Rf4 is an I-arylene group having a carbon number of J ~ 40 or a fluorine-containing arylene group having a scaly bond of a carbon number of 2 to 100, and Z1 is composed of an OH, a CH2OH, and a CHOH , Slow acid derivative, — functional group selected by the group consisting of SO3Η, carboxylic acid derivative, epoxy group or cyano group); among them, it is preferably CH2 = CFCF2ORf4 Ζ1 (in the formulas, and Rf4 for Ζ1 based on the same) and the structural unit derived More specifically, it is preferable to include CH2 = CFCF2〇CF -. Z1, CH2 = CFCF2OCFCF2OCF-Z1,

I I I cf3 cf3 cf3

2066-4683-PF (N); Tcshiau.ptd Page 23 572906 V. Description of the invention (19) CH2 = CFCF2CKCFCF2〇hCF — Z1, ch2 = cfcf2och2cf2 ~ z1,

I I cf3 cf3 ch2 = cfcf2och2cf2cf2ocf-z1,

I cf3 ch2 = cfcf2〇cf2cf2〇cf2-z1, CH2 = CFCF2〇- (CF2CF2〇hCF2-Z1 (the above, Z1 is the same as above), and other structural units derived from fluorinated ethylenic monomers. It is best to exemplify the structural unit derived from CF2 = CF0Rf4-Z1 (in the chemical formula, R f4 and Z1 are the same as above); more specifically, enumerate from cf2 = cfocf2cf2-z1, cf2 = cfocf2cf2ch2-z1 , CF2 = CF〇CF2CF〇CF2CF2 —z1

I cf3, cf2 = cfocf2cfocf2cf2ch2-z1

I cf3, CF2 = CF〇iCF2 ^ Zl, CF2 = CFOfCF2 ^ CH2-Z1, CF2 = CF〇CF2CF2OCF2—Z1, CF2 = CF〇CF2CF2〇CF2CH2 —z1, CF2 = CF〇CF2CF2CH2〇CF2CF2 — z1, CF2 = CF 〇CF2CF2CH2 〇CF2CF2CH2 — z1 (the above, z1 is the same as the above) and other unit derived from the monomer. In addition, as a fluorine-containing ethylenic monomer containing a functional group, CF2 = CFCF2-〇-R f-z1 > CF2 = CF-Rf-Z1,

Page 24 2066-4683-PF (N); Tcshiau.ptd 572906 V. Description of the invention (20) CH2 = CH-Rf-Z1, CH2 = CH〇-Rf -Z1 (above, one R f — is the same as above -R f —; Z1 is the same as above) etc .; more specifically, CF2 = CFCF2〇CF2CF2CF2-Z1, CF2 = CFCF2〇CF2CF2CF2CH2-Z1, CF2 = CFCF2〇CF2CF — Z1, CF2 = CFCF2〇CF2CF — CH2 — Z1

I I cf3 cf3 cf2 = cfcf2-z1, cf2 = cfcf2ch2-z1, ch2 = chcf2cf2ch2ch2 ~ z1, ch2 = chcf2cf2-z1,

ch2 = chcf2cf2ch2-z1, ch2 = chcf2cf2cf2cf2 ~ z1, ch2 = chcf2cf2cf2cf2-ch2-z1, CH2 = CH〇-CH2CF2CF2-Z \ ch2 = choch2cf2cf2ch2-z1 (the above and z1 are the same as above) and so on. However, in the case of using a group having a _OH group, a C00H group, and a-such as a 311 substrate, it is preferable to make the amount not to reduce the near infrared transmission 3 = early. Inside the inner wall of the heart ② 1w derived from a fluorine-containing ethylenic monomer that does not contain a functional group. This structural unit ② is able to further maintain the high sound block = position polymer (I) and its hardened matter. Infrared transparency

Yan 'is quite ideal. In addition, it is desirable to increase the glass transition point by selecting two: the mechanical properties of the polymer, the glass transition temperature, etc., especially H, and adjusting the structural unit M for copolymerization.疋 S can be used as the structural unit of the fluorine-containing ethylenic monomer ②, formula (4): is preferably chemical

2066-4683-PF (N); Tcshiau.ptd Page 25 572906 V. Description of the invention (21) —ecxi5x16—cx17 > (cx1%-) iTr ^ 〇 ^ Tr ^ R f 5 > τ-ζ2 (4) ( In the chemical formula, X15, X16 and X17 are the same or different and become Η or F; X17 is Η, F or CF3; hi, il and j are 0 or 1; Z2 is Η, F or Cl; Rf5 is carbon number 1 ~ 20 containing IL sulfinyl group or II containing sulfinyl group containing carbon bond of 2 ~ 100_). As a specific example, it is best to list C F 2 = C F 2, C F 2 = C Η 2, C F 2 = C F C 1, C F 2 = C F C F 3, / CF3

: CFH, CF CF2 = C \, CF2 = CF〇 (CF2) nF (η: 1 to 5), CH2 = C (CF3) 2,

CF

: CC12, CF2 = CF〇CF2CF〇-C3F

I CF, CH2 = CFfCF2) ^ Z2 (Z2 is the same as chemical formula (4) CH2 = CHOCH2- (CF2 ^ Z2 (Z2 is the same as chemical formula (4)) CH2 = CHOCH2-tC F2> ^ -Z 2 (Z2 is the same In the structural unit of the chemical formula (4). ③ When the structural unit t of an aliphatic ring having fluorine is introduced into the structural unit ③, the transparency can be improved, and the second one: the near-infrared transparency is further improved, and , $ Can get the south glass transition temperature of the Weng box to take over, 3 random prepolymer (I), expect the hardened material to become more nnn 10) 10) 10) and other monomers derived

2066-4683-PF (N); Tcshiau.ptd Page 26 572906 V. Description of the invention (22) The high hardness of the surface is ideal in this respect. The structural unit ③ of the fluorinated aliphatic ring is preferably the chemical formula (^ Λ ·) c < x'2 (5) {(CX19X20) nlCX2i cx22 (cx25x26) n3}-(θ) Π4 (〇) n5 /

Rf6 (In the chemical formula, X19, χ2〇, χ23, χ24, χ25, and χ26 are the same or different to form Η or F; X21 and X22 are the same or different to form Η, F, Cl, or CF3; Rf6 is 1 Fluorine-containing alkylene group of ~ 10 or fluorinated alkylene group having _ bond with carbon number of 2-10; n2 is an integer of 0 ~ 3; nl, n3, n4 and n5 are the same or different and become 0 or 1 Integer). For example: • 4CX21 — CX22 —

I I

Rf (in the chemical formula, R f6, X21, and X22 are the same as described above).

-f CF — CF4-I I 〇 〇

X

F F

4CF — CF4-I I 〇 〇

X CFa CF,

»FCF — CF — I I 〇 〇

X F CF,

2066-4683-PF (N); Tcshiau.ptd page 27 5729〇6 5. Description of the invention (23) 彳 CF—CF— -4CH-CH4-I I 〇 〇 CFoCl cf2ci cf3 cf:

+ CH — CH ·) -II 〇〇 > < r FF CICIO II cI cI 〇cI c 丨 〇IF c --〇-f cf2-cf-cf-cf2 ^ -II 〇cf2 CF2 \ Fo, 2 F cc \ ^ / 2 FF, c 丨 c > CX23X24 / \ -4CFCF CF different \ / O — CF2 c cf2 / \ -f CX19X20-CF CF >-

CF〇— O Ye C X19X20C F — C F C F 2 such as I I CF2—〇

〇CF3 弋 CF-cyI I 〇 〇 X F F -tCF-CF 十 / \ 〇 〇 / CF2-CF CF〇 (In the chemical formula, 'P, X2., X23 and X24 are the same as above) and the like. Examples of other fluorinated aliphatic cyclic structural units include

Page 28 572906 V. Description of the invention (24) 4CF2-

ο ο I I CF2 —C F I cf3 and so on. ④ Structural units derived from ethylenic monomers that do not contain fluorine. Structural units derived from ethylenic monomers that do not contain fluorine can be introduced within a range that does not deteriorate near-infrared transparency. s can be introduced into the structural unit ④ in order to improve the solubility in general solvents, or to improve the compatibility with additives, such as photocatalyst or hardener added in combination with the need. As specific examples of non-fluorine-based ethylenic monomers, α-enes are used in series: ethylene, propylene, butene, vaporized ethylene, vinylidene, etc., ethylene-based vinyl ester monomers: CH2 = CH0R, CH2 = CH0C0R (R: hydrocarbon group with 1 to 2 carbons), etc., allyl monomers: CH2 = CHCH2C1, CH2 = CHCH20H, CH2 = CHCH2C00H, CH2 = CHCH2Br, etc., allyl monomers: CH2 = CHCH20R (R: a hydrocarbon group having 1 to 20 carbon atoms), CH2, CHCH20CH9, CH9C00H, CHo ^ CHCHpOCHoCHCH, 〇

CH2 = CHCH2〇CH2CHCH2 OH OH, etc., acrylic or methacrylic monomers: Except acrylic acid, fluorenyl @ enoic acid, acrylates, methacrylates, maleic anhydride, maleic anhydride Acids, maleates, etc. From the viewpoint of transparency, the hydrogen atoms of these non-fluorinated ethylenic monomers are replaced with heavy gases.

2066-4683-PF (N); Tcshiau.ptd Page 29

572906 V. Description of the invention (25) The atomist is more ideal. ⑤ The early structure of the structure derived from the greasy monomer as the copolymerization component of the structural unit M is more ideal. ④) In addition to the structural unit, an alicyclic monomer structural unit ⑤ as the third component is also introduced; thereby achieving high glass transition temperature or two hardness. As specific examples of the alicyclic monomer ⑤,

(m is an integer of 0 to 3; A, B, C, and D are the same or different and become fluorene, F, Cl, C00H, CH20H, or a perfluoroalkyl group having 1 to 5 carbons, etc.) Derivatives, μ

And other alicyclic monomers, or derivatives in which a substituent is introduced into the foregoing. / In the fluorine-containing prepolymer (I) used in the present invention, the combination or composition ratio of the structural unit M (Ml, M2, M3) and the structural unit A can be determined by the combination of the structural unit M and the structural unit A. Become an amorphous group ° person

572906 V. Description of the invention (26) In the range of 25 weight at the rate of ϊΐ ϊΐ ，, the application and physical properties (especially glass transition temperature selective function (transparency, near infrared) Transparency), etc., and ΠB — as an essential component, the combination has the function of maintaining the near-infrared: M itself to the south to impart hardness, sexuality, and resistance: = dagger function. In addition, it also has The so-called feature that the refractive index can be controlled by adjusting the content of the structure j position M. Because the body (1) is a structure that contains many structural elements, the group = the end is only by the structure unit M (100 Mo The "I" compound can also maintain high near-infrared transparency. In addition, a hardened product with high hardening (crosslinking) density can be obtained at the same time, and high hardness, good abrasion resistance, and abrasion resistance can be obtained at the same time. And heat-resistant coating. In addition, 'S from the fluorinated prepolymer (manufacturer)' s construction unit "in the state of the construction unit's weight per unit of copolymer" can be improved by the foregoing examples. Infrared transparent high hardness ^ Μ Ϊ Ϊ: prepolymerized Ϊ I) In the state of the copolymer between the structural unit M and the structural unit A, the content of the structural unit M is a prepolymer (the total structural unit of D .. Hardened (crosslinked) to obtain hardened products with high hardness, good abrasion resistance, abrasion resistance, and good chemical resistance and solvent resistance, because 2066-4683-PF (N); Tcshiau.ptd 572906 five Explanation of the invention (27) Therefore, the content of the structural unit M is preferably 2.0 mol% or more, more preferably 5 mol% or more, and most preferably mol% or more. Particularly, heat resistance must be formed. For the use of the material for the light guide wave path of the hardened coating film with good transparency, low transparency, and low water absorption, it is preferable that the human unit of the structural unit M contains 10 mol% or more, and more preferably 20 mol%. Above, even more than 50 mole%. The upper limit is less than 0.00 mole%. Because of the fluorine-containing prepolymer () used in the present invention, the ratio of the structural unit M (even if the hardening site is increased) ), And also 9 near infrared transparency, so especially in light-guided waves The material-has ideal characteristics. In addition, the hardening fluorine-containing prepolymer (1) starts from visible light for optical communication to the near-infrared region and high transparency becomes a must state. It has a structural unit M The combination with the structural unit A can form a combination and composition of crystallinity, which is very important. Here, the so-called non-duality is the DSC analysis, at a temperature increase rate of 1 (rc / min conditions ::-determination ( (ASTM D3418-99), it is best to observe whether there is an endothermic peak caused by the actual purchase order, or it is best to show the heat of dissolution is 丨 j / g. In addition, the hardening fluorine-containing prepolymer (I) The fluorine content is 25% by weight or more. When the fluorine content is low, the transparency in the near-infrared region is low. In addition, when the fluorine content is low, the water-absorptive system also becomes high, so that it cannot be practically used as an optical material for optical communication and the like. For ^ materials and luminescent materials, the optimal fluorine content is 40% by weight

572906 V. Description of the invention (28) 2. The upper limit of the percentage of fluorine t depends on the composition of the fluorine-containing prepolymer (I), and m = the fluorine content rate when all the hydrogen atoms of the tongue have been replaced with fluorine atoms, which is about 75% by weight. : The molecular weight of the fluorine prepolymerized fluorene (I) can be selected from, for example, a number ranging from 500 to 100,000 in an average number of blades, preferably 1 000 500000 ', particularly preferably 2000. To 200,000. Sixth, when the sub-quantity is too low, even after hardening, the mechanical physical properties are likely to become inadequate ', especially the hardened material or the hardened film tends to become brittle and the strength is not f. If the molecular weight is too high, the solubility of the solvent tends to deteriorate, or when the film is formed, the film-forming property or the correctability tends to deteriorate, and the storage stability of the fluorine-containing prepolymer tends to become unstable. stable. For the use of the optical waveguide, the number average molecular weight is preferably selected from the range of 5000 to 10,000. The maximum value of the absorbance coefficient of the prepolymer (I) and the fluorine-containing prepolymer itself (before hardening) in the wavelength range of 1290 ~ 1 320nm and the wavelength range of 1530 ~ 1570nm, preferably less than lcnfl It is particularly preferable that it is not more than 0.5 cnri and is not more than 0.1 cm-1. In addition, the refractive index is preferably in a range of nd: 1.3 to 1. · 7. This adjustment can be performed by determining the type, content, and type of the structural unit a used in accordance with the requirements of the various structural units M. With these adjustments, selection of the core portion or the cladding portion in the optical waveguide type element described later can be performed. In addition, it is also a fluorine-containing prepolymer, preferably soluble in a general-purpose solvent, for example, it is preferably soluble in a ketone-based solvent, an acetate-based solvent, and an alcohol-based solvent.

Μ Page 33 2066-4683-PF (N); Tcshiau.ptd 572906 V. Description of the invention (29) Solvents, Fangxiang family solvents are few-this, S ~ ~ $ I η remaining, or soluble in A mixed solvent containing at least one of these universal bath agents. The so-called is soluble in general solvents, and the system is made in Shanghai and Shanghai; v π π 丄 is particularly thin and homogeneous. Inch: Minhao's film-forming fork pays enthusiastic results, even in terms of the productivity of the formation, it has become quite advantageous. In order to obtain the fluorine-containing prepolymer used in the present invention (", therefore, generally You can also use any of the following methods: 厶 Λ 和 古 VI 夕 留 胁 'A method • ① a method of preliminarily synthesizing a soap body with Υ for polymerization; and ② a

Polymers with other functional groups are converted into functional groups by high-resolution U compounds and introduced into functional groups Y1. "、 The method of polymerizing h but ΐ 'in ①' in order to obtain a slave-carbon double bond at the end of the side bond that does not react (harden), and a fluorine-containing prechain (I) with a carbon-carbon double bond in the side chain Therefore, it is necessary to cause the polymerization of only the double bond on one side by changing the double bond (becoming the double bond of the main chain and the double bond of the side chain) of the (co) polymerizable monomer species; In the method, the selection of the polymerization conditions for the fluorine-containing prepolymer having a carbon-carbon double bond in the side chain becomes difficult, and the side chain double bond itself in the obtained fluorine-containing prepolymer is hardened. Reactivity is not easy to become too high, so it is the method of ②. The method of removing ② is to easily obtain the fluorine-containing prepolymer of the invention without performing a hardening reaction, and simultaneously, the carbon-carbon double bond having high reactivity can be introduced to the side chain and / or the end of the main chain. From a viewpoint, the method of ② is an ideal method. '

2066-4683-PF (N); Tcshiau.ptd 572906 V. Description of the invention (30)-Even in the method of ②, as described later, for example, the following methods are best used: After synthesizing the structural unit M of the chaotic monomer-containing organic group Y3 and the fluoropolymer composed of the structural unit B of a monomer capable of copolymerizing with N according to the needs, after synthesis, then, Unsaturated carboxylic acid or its derivative: A reaction takes place and a carbon-carbon double bond is introduced into the side chain and / or the end of the main chain of the polymer. The detailed description is given below as an example. First, the chemical formula (2): — ~~ (-Β ^ — (2) [In the chemical formula, the structural unit N is the chemical formula (ν) — (-CX'X2 —CX3-) — (N) (CX4x5 ^-< -C ^ 〇) b (〇) __ Rfl (In the chemical formula, X1 and X2 are the same or different to form Η or F; X3 is Η, F, CH3 or CF3; X4 and X5 are the same or different to form η, F or CF; Rfi is a fluorine-containing alkyl group having a slave number of 1 to 40 or a fluorine-containing alkyl group having an ether bond with a carbon number of 2 to 100, and a combination of 3 γ3 and a carbon number] ~ (ΐ〇〇, αorganic group) organic group; "is an integer of 0 to 3; ... is ΪΓί: the same as 0 or 1) is made of a fluorine-containing ethylenic monomer, and 3 has a radical The structural unit and the structural unit B are due to the structure given: the unit of two = the base of the feminine monomer and the copolymerizable monomer qq ^ not i contains 0.1 to 100 mole% of the structural unit N and 0 structure The polymer B containing the base group of the unit B and the unsaturated Lai or its derivative are produced by an acetic acid reaction.

572906 V. Description of the invention (31) Fluorine-containing prepolymer (I). -In the manufacturing method of the fluorinated prepolymer (j), it is preferable that specific examples of the fluorinated polymer (ffi) containing a hydroxyl group in the precursor shown in the chemical formula are separately described Each of the structural units M corresponding to the previously exaggerated f: 3 fluorine prepolymerized fluorene (I) is replaced by a part γ1 containing a carbon-carbon double bond by a part Y3 containing a 011 group. The best ΓΓΛ can use the same In the foregoing structural unit a, the carboxylic acid or ^: of a middle carbon-carbon double bond is widely used, such as an unsaturated m acid or a derivative thereof.

'R CH2 = c vC〇〇h (in the chemical formula, R is η, an anhydride of a CH2 carboxylic acid, or CF3 or C1) or these

/ R CH2 = c

\ c〇X (In addition to the compounds in the chemical formula, but also acid monoalkyl esters, etc., R is the same as the maleic acid listed above; x is C1 or ρ) acid maleic anhydride, Cis-butene_ Among them, when the reaction is carried out and the unsaturated carboxylic acid function is used, the polymerization can be prevented, and the gelation of the material at room temperature can be prevented, because 572906 V. Description of the invention (32) Therefore, It becomes quite ideal. Specifically, ’especially the best

FI CCOF ch3 C Η 2 = CHCOC 1, C Η 2 = c C 〇c 1, c Η There is no method for reacting α, point_unsaturated carboxylic acid halides in a fluoropolymer (m) containing a hydroxyl group. Although it is specifically limited, a fluoropolymer containing a hydroxyl group (dish) can usually be dissolved in a solvent, and the fluoropolymer containing a hydroxyl group (a curse) can be dissolved in _200c ~ 4 (rc The reaction between 1st and 2nd degrees is to mix and react with 'synthesis α, unsaturated acid acid halide. In this reaction, HC1 or bite is produced as a by-product due to the reaction. However, for the purpose of capturing these HC1 or HF, Therefore, it is better to add an appropriate base. As the base, a series of tertiary amines such as pyridine, N, N-difluorenylaniline, tetramethylurea, triethylamine, and metal magnesium are used. At 1, the coexistence is also used to prohibit the polymerization of α, 々-unsaturated acid in the raw materials or the carbon-carbon double bond in the obtained prepolymer to inhibit the polymerization reaction. As a prohibition agent, a series of hydrogen lifts Quinone, t-butylhydroquinone, hydroquinone monofluorene basis test, etc. By the conventional methods, Ethylene monomer N, which is a unit of hydroxyl group, and monomer B, which is a copolymerization component in the used state, are subjected to (co) polymerization in order to obtain a fluorine-containing fluorine group containing an unsaturated carboxylic acid or a hydroxyl group before reacting the derivative thereof. Polymer (dish). The polymerization method can use radical polymerization method, anionic polymerization method and cationic polymerization method.

2066-4683-PF (N); Tcshiau.ptd Page 37 572906 V. Description of the invention (33) etc. Among them, in order to obtain a polymer (melon) containing a hydroxyl group, from the viewpoint that the fluorene group tf has good compatibility, Even from the viewpoint of easy control of the composition of the obtained polymer or the quality of the knife, and the viewpoint of easy industrialization, it is preferable to use a radical polymerization method for each of the monomers exemplified. In order to start the radical polymerization, it is possible to enter the " T device in a free-radical manner without any restriction, but, for example, organic or non-radical polymerization initiator, heat, light or ionization Radiation and so on, and start radical polymerization. The morphology of polymerization can also use solution polymerization, ^ 2 field suspension polymerization and emulsion polymerization. In addition, the molecular weight is determined by polyisocyanate, W ^ f concentration, the concentration of the polymerization initiator, and the severity of the chain transfer agent I. The composition of the copolymer can be controlled by the composition of the soap body loaded. Even if the fluoroprepolymer (j) is used alone as the material for the light guide wave path, 2% of the light is passed to the present invention, and the light is free to be added to become the active energy ray. Based initiator (D-1) or photoacid hairpin (Π -2) to form a photocurable composition. Agent The fluorine-containing prepolymer (j) in the material of the present invention is in the side chain and / Or the polymer main bond has 25% by weight of non-crystalline & double bond at the end of the main bond, and the fluorine content is at least 3 fluorine prepolymer. The same as the foregoing. ^ Ai specific activation energy ray hardening initiator (Π), electromagnetic waves in the wavelength range below 35nm are; two activation energy rays such as lines, x-rays, etc., most:

2066-4683-PF (N); Tcshiau.ptd Page 38 572906 V. Description of the invention (34) Free radicals or cations (acids), etc., and the hardening of the carbon-carbon double bond of the hair body (crosslinking reaction starts) The fluorine-containing prepolymer uses a catalyst function that generates free radicals by ultraviolet rays, and generally generates free radicals. (Acids), especially when used as the photoconductive resin composition of the present invention, it can be used. Μ The hardening reaction is carried out by the light-hardening fluorine of the dual-use material. It does not require = = =; it is easy to start the temperature and perform the hardening reaction. Therefore, it can be deformed and decomposed at a lower temperature than heat. The coloring ^ beautiful ^ ° has low heat resistance, and it is easy to be changed from the aspect of the base material of Cangxigu A ^ — 1 color, such as a transparent resin substrate, etc., which becomes quite ideal. The initiator (π) is based on the type of the carbon-carbon double bond (free radical reaction or cationic (acid) reactivity) in the fluorine-containing prepolymer (I), and the type of active energy rays used ( The wavelength range, wavelength, and irradiation intensity are selected appropriately. The initiator (photoradical generator) for curing the fluorine-containing prepolymer (I) having a free radical reactive carbon-carbon double bond using an activation energy ray in the ultraviolet region can be exemplified by the following: B Benzene series-acetophenone, gas acetophenone, diethoxy acetophenone, hydroxyacetophenone, α-aminoacetophenone, etc., benzoin series-benzoin, benzoin methyl ether, benzoin ethyl ether, Benzo isopropyl ether, benzoin isobutyl ether, benzyl difluorenyl ketal, etc., dibenzyl alcohol-dibenzoyl enzyme, phenyl benzyl benzoic acid, benzyl benzoic acid, 4-phenyl diphenyl Formic acid, hydroxybenzyl alcohol, hydroxypropyl diphenyl alcohol, acrylated dibenzoyl enzyme, tetramethyldiaminobenzophenone, etc., thioxanthone-thioxanthone, chlorothioxanthone, Dithioxanthone, diethyl

2066-4683-PF (N); Tcshiau.ptd 572906 V. Description of the invention (35) thioxanthones, dimethyl thioxanthenes, etc., sodylphosphonium oxide, glyoxal, 3-fragrant% = Alpha fluorenyl oxime ester, fluorescein, anthrone and the like. Fragrant ketone, 2-ethylanthone, camphor In addition, a photoinitiator such as an amine or the like may be added in accordance with the need. Code type, sub-%. In addition, as a hardened fluorine-containing prepolymer (;;) with a cationic carbon double bond (; [] 的 私 $ 丨 彳 止) reaction 14 stone counter_ can be exemplified by: Iodine 〇 * "Acid generators", salts, ammonium salts, arsenic salts, etc., m-compounds, n-based compounds, sulfonates, sulfonates and alkyl sulfonates , I-imine compounds, diazomethane compounds, etc. "Others-Code 醯 In addition, as a radical reactivity ^ ^ the chemical formula -0" = Qing ,, :: 1 double bond, such as the former carbon -Carbon double bonds, which are listed, for example, ^ is a cationic reaction-〇CH = CH2, 'ideally γ1 is used in the light guide of the present invention ^ by fluorine-containing prepolymer (I) and activated As described on the side of J_, it is necessary to coat and mix a chemically fluorinated resin composition and a hardening initiator to form a solvent described later, and a hardener is included in these. 3 fluororesin composition coating liquid, also added as a hardener, it is best to advance the radicals or acids of unsaturated bonds3: radical polymerization with only one or more carbon-carbenoic acid monomers ^ Second, specifically, the series of C & Cs: Yang Fang, Premature Body, Vinyl Ether Monomer, etc. 2066-4683-PF (N); Tcshiau.ptd Page 40 572906

Ionic polymerizable monomer. These monomers may be either monofunctional or monofunctional, and may be monomers having two-functions. The so-called hardeners which have many carbon-carbon unsaturated bonds in the cross-links are those which can be reacted by the radicals or cations generated by the reaction between the active energy ray hardening initiator and light and the like in the materials of the present invention. The carbon-carbon double bonds of the fluorine-containing prepolymer (〗) in the material of the present invention are summed together, so as to facilitate the transaction. , Λ are monofunctional acrylic monomers, except acrylic acid, propyl esters, methacrylic acid, fluorenyl acrylates, α-fluoroacrylic acid, fluoroacrylic acid esters, maleic acid, maleic anhydride In addition to cisbutadienyl esters, those having epoxy groups, hydroxyl groups, carboxyl groups, and the like (formaldehyde = ^ acrylates, etc. ^); where 'in order to maintain the near-infrared transparency of the hardened material at a low degree Therefore, ', is preferably an acrylic monomer having a fluorocarbon group, for example, it is preferably

X

I ch2 = c-coor f 10 (X is H, CH3 or F; Rf1G is a fluorine-containing alkylene group having 2 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100) The compound shown. Specifically, the dry f CH2 = C — C〇CH2CH24CF2> ^ F, CH2 = CCOOCH2CH2-eCF2h-F,

2066-4683-PF (N); Tcshiau.ptd Page 41 572906 V. Description of the invention (37)

X X

I I CH2 = C — C〇〇CH24CF2Mi, ch2 = cc〇ch2cf3, X x

I I CH2 = C — C〇〇CH2 ^ € F2> t «, ch2 = cco〇ch2 (cf2) 6h, X cf3 x cf3 II II ch2 = c-cooch, CH2 = C_C〇〇C-CF3,

I I cf3 cf3 x cf3

I I CH2 = C — C〇CH24CF2) tCF,

I cf3 CH2 = C-COOCH2CF- (OCF2CF> irOC3F7 (above, X-based H, CH3 or F; n is an integer of 1 to 5)), etc. As polyfunctional acrylic monomers, it is generally known to use diols, Compounds such as trihydric alcohols, tetrahydric alcohols, and the like substituted with hydroxy groups of acrylates, methacrylates, and α-fluoroacrylates. Specifically, 1,3-butanedi Alcohols, 1,4-butane diols, 1,6-hexane diols, diethylene glycol, tripropylene glycol, neopentyl glycol, trishydroxymethylpropane, pentaerythritol, Dipentaerythritol and other polyhydric alcohols, which are substituted with two or more hydroxyl groups, and are substituted with any one of an acrylate group, a fluorenyl acrylate group, and an α-fluoroacrylate group. In addition, it is particularly capable of maintaining a high degree of hardening. Near infrared transmission

2066-4683-PF (N); Tcshiau.ptd Page 42 572906 V. Description of the Invention (38) —

In terms of clarity, it may be preferable to use two or more hydroxyl groups of a polyhydric alcohol having a fluorinated alkyl group or an oxyalkylene group to substitute an acrylate group, a fluorenyl acrylate group, and α to fluoroacrylic acid. Polyfunctional acrylic body of ester group. As a polymer example, it is best to list

R f n-CH-CH2OH, r f i1-CH2OCH-CH-CH2OH 〇H OH

R

I H〇CH2C-C〇〇CH2CH-R f 11

II ch2oh oh (above, Rf11 is a fluorine-containing alkyl group having 1 to 40 carbon atoms; R is H or an alkyl group having 1 to 3 carbon atoms), H〇—CH2 — R f 12 — CH2〇H, HO-CH2CH ~ CH2-Rf12-CH2-CHCH2OH,

OH OH I i

H〇-CH2C_C〇〇CH2CH — Rf12 — CHCH2〇C ——CCH〇OH

III II I CH2OH oh oh och2oh (above, Rf12 is a fluorine-containing alkylene group having 1 to 40 carbon atoms; R is h or a carbon group having 1 to 3 carbon atoms), etc. A structure in which two or more via groups are substituted with an acrylate group, a fluorenyl acrylate group, or an α-acrylic acid ester group. In addition, in using these exemplified monofunctional, polyfunctional acrylic monomers,

2066-4683-PF (N); Tcshiau.ptd Page 43 572906 V. Description of the invention (39) The material of the present invention as a hardener The hardening reactivity is good γ Yazhong, especially from vinegar compounds. 5 [is preferably monofluoropropionic acid. In the material for optical waveguides of the present invention, the amount of live addition is used in conjunction with the fluorine-containing prepolymerized stomach (the content of hardening initiation double bonds and the use of hardening agents). 1) The carbon-to-carbon content is appropriately selected due to the amount and intensity (intensity, time, etc.) of the starting agent and the activating agent used: type or irradiation energy; ; 1, parts by weight, = poly di = 0. 01 to 10 parts by weight I 1 part by weight, preferably in detail, relative to the fluorine-containing prepolymer in the state of using a hardener, 10 moore %. The content of the carbon-carbon double bond contained in the 3, the prepolymer of 3 fluorine (1) the Moore number of the carbon-carbon unsaturated bond, and the γ of the hardener are preferably γ. 20 mol%, best ideal: 5 · ～ ι 02 The material of the present invention can be compounded in addition to the aforementioned compounds, and various additives are added within a range that does not reduce the near-infrared transparency. Examples of such additives include correction agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, and reinforcing agents. ΙΗ Η 2066-4683-PF (N); Tcshiau.ptd p. 44

572906 V. Description of the invention (40) The light of the present invention is dispersed in a solvent. Those who use or disperse fluorine-containing prepolymers here) and add additives according to their needs do not specifically decompose the fluorine-containing prepolymers (as such a solvent, methyl cellosolve solvent; difluorenylethyl ester, ethylacetamidine Ethyl butyric acid, methyl keto acid, 3-methoxy 2-hydroxyisoethyl butyl propylene glycol monoethyl monomethyl ether acetate alcohol monobutyl ether acetate alcohol solvent; 2-hexane solvent Methanol, solvent, mixed solvents such as methylbenzene, dimethyl ether, etc. In addition, in order to also be able to cooperate with the need for guided wave paths, the supply is used as a hard limit (I) to add strength to the solution. Solvents are esters, acetates, diacids, acid salts, butyric acid, ethyl ethyl diacetate, etc., ethyl, propylene ethyl salts, dipropylenes, cyclohexanol, benzene and other aromatic compounds. Increase the fluorine content. The use of fluorine materials is a solvent that is made by dissolving or manufacturing various components used in the optical waveguide as described later. It can be a uniformly dissolved and activated energy ray hardening initiator (n-forming agent, corrector, light stabilizer, etc.). In addition, it is particularly preferable to uniformly dissolve, for example, methylcellosolve, ethylcellosolve, ethylcellosolve, acetate, etc., as the cellosolve is ethylpyruvate, ethyl-2-hydroxybutyrate, etc. Acid acetic acid, amyl acetic acid, ethyl butyric acid, lactic acid, 3-methoxymethyldiethylfluorenyl ketone acid, 2-hydroxyisomethylbutyric acid, solvents; propylene glycol monofluorene Ether, propylene glycol monobutyl scale, propylene glycol monool monoethyl bond acetate, propylene ethylene dione, fluorenyl amino ketone, etc. Alcohols such as keto alcohols such as 2-heptanone, isopropanol, butanol, etc. are soluble aromatic hydrocarbons or two of these solvents are prepolymerized. (I) is a solvent.

2066-4683-PF (N); Tcshiau.ptd Page 45 572906

V. Description of the invention (41) As a fluorine-based solvent, except for example, CH3CC12F (HCFC-141b), CF3CF2CHC12 / CC1F2CF2CHC1F mixture (HCFC-225), All-in-a-house, Perfluoro (2-butyltetrahydrofuran) In addition to methoxy-nonafluorobutane, 1,3-bistrifluorofluorenylbenzene, etc., H (CF2CF2 ^ tCH2〇H (η: an integer of 1 to 3),

F (CF2 ^ CH2OH-1 (Π: integers from 1 to 5), cf3ch (CF3) 0H, and other fluorine-based alcohols; benzodiazepines, perfluorobenzene, perfluoro (tributylamine), C1CF2CFC1CF2CFC12, etc. ^ These fluorine-based solvents can be used singly or as a mixture of more than one solvent of non-fluorine-based and cereal-based, non-fluorine-based and fluorine-based. Even in these solvents, the From the viewpoint of productivity, etc., ketone-based solvents, acetate-based solvents, alcohol-based solvents, aromatic solvents, etc. are preferred. The second aspect of the present invention relates to a kind of (1), or for the active energy ray hardening initiator (n)

A component for an optical waveguide composed of a hardened material composed of the formed composition by light curing. L The maximum value of the absorbance coefficient of the hardened product in the wavelength range of 1 290 to 1320 nm and the wavelength range of 1 530 to 1 nm is a member for the optical waveguide of the invention of βcnrl, which constitutes the optical waveguide The mold element is formed on the substrate. Here, the so-called optical waveguide type

572906 V. Description of the invention (42) It is connected between the optical functional elements through the light guide wave path. Because of & the light guide wave is composed of the core αP and the cladding part. On the other hand, the so-called “optical functional element” is used for optical communication signals to display elements such as amplification, wavelength conversion, and wavelength selection of photosynthetic and demultiplexing wavelengths. There are also various forms, but it is also used for photosynthetic demultiplexing or optical amplification Guided wave path type functional element. In this case, the element system b is also formed of a core portion and a cladding portion. One piece of the present invention can also be used on any core portion and cladding portion, and it is also possible to use the member of the present invention only on the first portion or the cladding portion. In addition, various functional compounds such as non-linear optical materials or fluorescent organic pigments, light lithography materials, etc. can be used in the components of this issue, and the core material can be used as a waveguide-type functional element. . Further, it is more preferable that both the core portion and the cladding portion are those hardened with a fluorine-containing prepolymer. That is, the third aspect of the present invention relates to an optical waveguide type element including the aforementioned second member of the present invention. / In a state where the optical waveguide type element has a ridge portion and a cladding portion, the refractive index of the core portion must be higher than that of the cladding portion, but the difference in refractive index between the core portion and the cladding portion is It is preferably at least 0.003, and more preferably at least 0.001. Since the materials and components of the present invention can control the refractive index in a wide range to a wide range, the choice of materials is wide. For optical waveguide devices, the width of the core is preferably 5 to 50 °. In addition, the height of the core is preferably 5 to 50 zzm ^ The width and height accuracy of the core is preferably 5% or less, more preferably 1% or less. 0 Figure 1 is a schematic cross-sectional view illustrating a typical optical waveguide type element. 47 page 47

IH 2066-4683-PF (N); Tcshiau.ptd 572906, Invention Description (43) Structure. Symbols 1 are substrates, 2 are cores, and 4 and 5 are cladding portions. Such an optical waveguide type element is used to connect optical functional elements, and the light emitted from the end of a certain optical functional element is contained in the core portion 2 of the optical waveguide type element, such as the core portion 2 and the cladding portion 4, The interface between 5 is reflected repeatedly, and at the same time, it is transmitted to the end of the light function element on the other side. The form of the light-conducting element is an appropriate form such as a flat type, a band type, and a wave crest type. The substrate material of the optical waveguide device is not particularly limited. Suitable materials such as metals, semiconductor materials, ceramics, glass, thermoplastic resins, and resins can be used. ... q Fig. 2 shows an example of a manufacturing operation of an optical waveguide type element using the material of the present invention. The optical waveguide type element is manufactured using light micro. First, as shown in FIG. 2 (a), a cladding portion 4 is formed in advance on the substrate w: to form a film 3 of the material for an optical waveguide of the present invention (forming a core portion). When forming the material film for the optical waveguides of the cladding portion 4 and the core portion, it is preferable to apply these material solutions by application such as spin coating, cast coating, etc., especially It is preferably spin coating, = the various material solutions described above, and is preferably dissolved in a solvent in accordance with the thickness of each layer of the film, and then is performed by, for example, a pore size of 0.2. Filtration and preparation. The ideal concentration of various material solutions is not dependent on the coating method, but, as far as the resin forming the core is generally used, the solvent is generally equal to 5 to 1000 g for the solvent. It is preferably 30 ~ 500g, and the cladding material is; s' is generally 1 ~ 100g, particularly preferably 30 ~ 50Og.

572906 V. Description of the invention (44) In addition, the ideal concentration of the radiation-sensitive material is generally 100 to 500 g for 1 liter of solvent, and particularly preferably 300 to 400 g. The solvent used for the solution preparation is suitable for the foregoing. ^ Next, as shown in FIG. 2 (b), for a fluorine-containing prepolymer, an active energy ray 7 is irradiated through a mask 6 ′ in the shape of a conventional pattern. Then, pre-sintering is performed as needed. During photo-hardening, the carbon-carbon double bond of the fluorine-containing prepolymer (I) in the material for the optical waveguide of the present invention is 'polymerized' between molecules so that the carbon-carbon double bond in the polymer is reduced or disappear. As a result, not only the hardness of the resin becomes higher, the mechanical strength is improved, or the heat resistance is improved, but even the solvent dissolved before the hardening becomes insoluble, and it also becomes insoluble for a large number of other various solvents. That is, it functions as a photoresist material. Then, by using an appropriate solvent, the uncured fluorine-containing prepolymer 'is dissolved to facilitate the formation of the core portion 2 having a predetermined pattern shape as shown in circle 2 (c). The optical waveguide type member can also be used directly only in the form having the core portion 2 formed as described above, but after the core portion 2 is formed, as shown in FIG. 2 'It is best to form Cladding section 5. It is preferable to apply the material solution of the cladding portion 5 by using spin coating, cast coating, roll coating, etc., so as to form the cladding portion 5, particularly, spin coating is preferable. In addition, the material solution of the cladding portion 5 is also preferably: after being dissolved in the solvent, for example, filtered and prepared by He Ke with a pore size of about 0.2 #m. Going forward, in addition, in the state where the package is made of the material for optical waveguides of the present invention, it is used as a solvent for the preparation of these resin solutions.

572906 V. Description of the invention (45) List the listed solvents in the state of the aforementioned core portion 2 or cladding portion 4, for example. In addition, when using a core material without light curing, it is necessary to use a radiation-sensitive material. In this state, after the radiation-sensitive material is further coated on the core material, and then, after the radiation is transmitted through the pattern, it is necessary to perform a silylation treatment and / or a germanium alkylation treatment and then Reactive ion etching for dry development. Such a process is very complicated, and it becomes a cause of rising costs. Next, the present invention will be described by citing synthesis examples and examples. However, the present invention is not limited to such examples. Synthesis Example 1 (Synthesis of homopolymer of fluorinated allyl ether having 0H- group) In a 100 m 1 glass four-necked flask equipped with a stirring device and a thermometer, king fluorine 1- (1,1 , 9,9-tetrahydro-2,5-bistrifluoromethyl- 3 6-dioxonanol), a CH-

CFCF2〇CFCF2〇CFCH2〇H

CF

I CF 2 0 · 4 g and [H + CF2CF2) yC〇〇3y 8.0% by weight perfluorohexane solution 22g, after sufficiently nitrogen substitution, and then under a nitrogen flow, 20 'for 24 hours to generate tritium High viscosity solid. -While stirring, the obtained solid was dissolved in diethyl ether, poured into perfluorohexane, and separated and vacuum dried to obtain a colorless and transparent polymer 17.6 g. °

2066-4683-PF (N); Tcshiau.ptd Page 50 572906

When the polymer was analyzed by 19F-NMR, 4-NMR analysis, and IR analysis, it was learned that the fluorine-containing fluorine-containing dilute propyl group was used as the structural unit and had a hydroxyl group at the end of the side chain. polymer. In addition, the number measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 9,000 and the average molecular weight was 22,000. = Example 1 (Synthesis of hardening fluorine-containing prepolymer (I) having α-fluoropropenyl group) In a 200-ml four-necked flask equipped with a loop cooler 'thermometer, a stirring device, and a dropping funnel, 80 ml of diethyl ether, 5.0 g of a fluoro-containing allylic ether-containing individual polymer obtained in Synthesis Example 1 and 5.0 g of fluorene ratio, and water-cooled to 5 ° C or lower. At the same time, under the air current, it was dripped in about 30 minutes to dissolve α-fluoropropionic acid gas (ch == CFCOF) 1.0g in 20 ml of diethyl ether. 2 After the dripping is completed, raise the temperature to room temperature, and continue to instill for 4.0 hours. The ether solution after the reaction was placed in a separating funnel, and washed repeatedly with water, 2% hydrochloric acid, 5% NaC 1 and water, and then dried with sulfuric acid. Then, the ether solution was separated by filtration to obtain a curable fluorine-containing polymer. When investigating the hardenable fluoropolymer by 19F-NMR analysis, it was found that Of CF = CH2 group-containing dilute propyl group / OH group-containing fluoro allyl ether = 40/60 mole% copolymer.

2066.4683-PF (N); Tcshiau.ptd Page 51 572906 V. Description of the invention (47) When performing IR analysis on those coated on NaCl plates and becoming cast films at room temperature, carbon-carbon double bonds were observed The absorption is ^ "㈣", and the absorption at C = 0 group is 1 770 cm-1. Dotsugi Example 2 (Synthesis of sclerosing fluorine-containing prepolymer (α) with α-fluoropropenyl group) Α In addition to using α-fluoroacrylic acid fluoride (ch2 = CFC0F) 0 · 65g and mouth ratio bite 1 Except for 0 g, the rest is the same as in Example 1, and a hardenable fluorine-containing prepolymer (ether solution) was synthesized. When investigating by 19F-NMR, it was found that -〇iCF = fluorinated allyl ether containing CH2 group / ° air-containing dilute ether containing OH group = 30/70 mol% Copolymer. It was confirmed that in the IR analysis, the absorption systems of the carbon-carbon double bond and the c = 0 group were all at the same position as in Example 1. Real m (Synthesis of hardenable fluorine-containing prepolymer (1) with α-fluoropropenyl fluorenyl group) ^ α: Gas propane fumes (CH2 = CFC〇F) 0.352 and pyridine · 3g Other than that, it is the same as the actual prepolymer (I) (transformation solution). Mouth hardening "At the time of investigation by 19F-NMR-〇CCF = fluorinated allyl ether containing right 右 II ^ LH2 group / 4 Allyl ether = 15 to 85 mole% copolymer. Both the carbon-carbon double bond and the C = 0 absorption group in the two knives are at the same position as in Example 1. U 丞 I and sigh you white in Example 4 (Physical evaluation of a light-hardened film that becomes a light-guiding member for a leather road

572906 V. Description of the invention (48) (1) Modulation of materials for optical waveguides The hardening fluorine-containing prepolymer manufactured in Example 1 is dissolved in methyl ethyl ketone (MEK) and adjusted to the polymer concentration 50% by weight. To 10 g of the obtained curable fluorine-containing prepolymer solution, a solution of 2-hydroxy-methylphenylacetone dissolved in 1% by weight as an active energy ray hardening initiator (photo radical generator) was added. 7g, to obtain a material for light guide waves. (2) Manufacture of thin film for optical waveguide materials

Using an applicator, apply the material for optical waveguides (50% mek solution of fluorine-containing prepolymer) prepared in (1) on the polyester film, so that the film thickness after drying becomes a predetermined value. The thickness (about 1mm and about 100em) was vacuum dried at 50 ° C for 10 minutes. Then, the obtained cast film was peeled from the polyester film to a thickness of about 1mm and about 100mm. Materials for optical waveguides in the form of left and right unhardened films.

(3) Production of a hardened film by light irradiation ^ After drying the film produced in (2) above, a high-pressure mercury lamp was used, and the film was subjected to room temperature at 3000 mJ / The intensity of cMU is irradiated with ultraviolet rays and photocured to obtain a cured film. (4) Measurement of physical properties of cured film The following physical properties were evaluated for the obtained cured film. ① Measurement of absorbance coefficient Using a self-recording spectrophotometer (manufactured by Hitachi, Ltd.)

2066-4683-PF (N); Tcshiau.ptd Page 53 572906 V. Description of the invention (49) U-3410) 'Measurement of a sample with a thickness of approximately ^^ at a wavelength of 300 to 1700 nm (hardened film ) Of the spectral transmittance curve. Based on the obtained spectrum, the value of the absorbance coefficient was calculated according to the following formula: • Absorbance coefficient = absorbance / thickness of the sample. The results are shown in Table 1. ② Measurement of refractive index Using an Abe refractometer, the refractive index at 25 and 5500 nm was measured on a sample (hardened and hardened film) having a thickness of about OO β m. The results are shown in Table 丨. ③ Thermal characteristics (DSC) below the 9th line The thermal characteristic peaks under the conditions of using a differential thermal calorimeter (Shimadzu Corporation Co., Ltd.) at a temperature speed i1 (rc " clock) become non-crystalline. To the clear crystalline melting point wave ④ Solvent resistance evaluation film Female two eyes 2 Observation of the hardening film thickness of about 1 mm after holding in acetone at room temperature for 24 hours: Evaluation of sigh The state of the film is based on the following criteria.

〇 X It is believed that there is no change in appearance and it is dissolved in acetone. The results are shown in Table 1. ⑤ Evaluation of financial and thermal properties Visually observe the shape change of the hardened film at 150 t for 8 hours: X Dali 〇 · I think there is no change in appearance,

2066-4683-PF (N); Tcshiau.ptd Page 54 572906

x. The film could not maintain its original shape. Examples 5 to 6 show the results in Table 1. Except that the fluorine-containing prepolymer shown in Table 1 (produced in Implementation j and produced in Example 3) was used instead of the gas-containing prepolymer having α-fluoropropenyl group obtained in Implementation m, the rest The film was produced in the same manner as in Example 4 to evaluate the cured film. The results are shown in Table 1. In addition, when the thermal characteristics were investigated by DSC, it was confirmed that the thin films after curing were all non-crystalline. Comparative Example 1

As for the uncured film of Example 4 which was not irradiated with light, the physical properties were evaluated in the same manner as in Example 4. The results are shown in Table 1.

-——

2066-4683-PF (N); Tcshiau.ptd Page 55 ^ J 572906 V. Description of the invention (51) Table 1

Example 4 Example 5 [Example 6 Comparative Example Prepolymer Example 1 Example 2 Example 3 Example 1 -0 (C = 0) CF = CH2 group containing child 40 30 15 40 Fluorine content rate (¾ 57 58 58 57 Activated energy ray hardening initiator 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methyl Ratio of phenylacetone year to polymer (% by weight) 2.1 2.1 2.1 2.1 UV irradiation (mJ / cm2) 3000 3000 3000 Unirradiated f kg Emissivity before hardening after hardening 1.362 1.366 1.359 1.364 1.356 1.361 1.362 Absorbance coefficient (cm -i) 1310nm 1550nm 0.040 0.13 0.043 0.11 0.047 0.079 0.040 0.12 Solvent resistance 〇〇-〇X Heat resistance 〇〇 ~~ δ ~ X; 1 'J AU, confirmation of the hardening reactivity by Yadao 斫) (1) The preparation of the material for the optical waveguide (the fluororesin composition for coating) was used in the four-stroke operation of the hardenable prepolymer (j) obtained in the example, and the coating composition (light The ray == the amount of polymer concentration and activation energy shown in Table 2 (2) Production of IR analysis film Using an applicator (applicat〇r), the coating application point ^^ .. ^ is applied on the ^ s film, "applied before coating, and formed into", so that the film thickness after drying is about 1 〇 ⑽ 572906 V. Description of the invention (52) After drying at about 50 ° C for 5 minutes, the obtained coating film was peeled off from the polyester film to obtain an unhardened cast film. (3) Measurement of hardening reactivity by 1 R analysis When performing IR analysis of the aforementioned unhardened film, absorption of carbon-carbon double bonds in the polymer was observed at 1 661 cm-1. (4) Hardening The measurement of the reaction rate focuses on the absorption of carbon-carbon double bonds, observes the change in the absorption intensity after light irradiation, and calculates the hardening reaction rate according to the following formula: 1661 cm before the light irradiation, and 1661 cm after the high light irradiation. The peak height of 1 x 100% For the irradiation with the irradiation shown in Table 2 ^ 'Ultraviolet irradiation, the amount' is calculated by using the high-pressure mercury lamp used in the above formula, at room temperature, the amount of (2) obtained Unhardened film, @ to hardened film. Also, change the exposure, The curing reaction rate. The results are shown in Table 2.

572906

V. Description of the invention (53) Table 2 Bao Shi Example 7 Example 8 Xi Example 9 Comparative Example 10 Fluorinated Hardening Polymer Po Example 1 Example 2 Example 3 Example 1 10 (C = 〇) CF = CH2 group content (Moore X) 40 40 40 40 Solvent MEK MEK ΛΛΕΚ ΜΕΚ Polymer concentration (weight? 6) 8 β 8 8 Activated energy ray hardening from $ hetero! 1 2-hydroxy-2-methyl 2- Ratio of hydroxymethyl 2-hydroxy-2-methyl-2-hydroxy-2-methylphenylacetone phenylacetone phenylacetone phenylacetone to polymer (% by weight) 4.2 2.1 1.0 0.2 Hardening reaction rate (%) UV irradiation Amount 100 (mJ / cm "100 (disappearing) 60 45 34 500-62 60 44 1500 — 100 (disappearing) 74 55 Example 11 (of a hardening fluorine-containing prepolymer (I) having an α-fluoropropenyl group) Synthesis) Except that α-fluoroacrylic acid fluoride (CH2 = CFC0F) 2. Og and pyridine 2. Og were used, the rest was the same as in Example 1, and a hardenable fluorine-containing prepolymer (I) (ether solution) was synthesized. When investigating this fluorine-containing prepolymer by 19F-NMR analysis, it was found that _iCF = fluorine-containing allyl ether containing CH2 group / ° H-containing fluorine-containing dipropyl ether = 8 4/16 mol% copolymer. It is confirmed that the absorption of the carbon-carbon double bond and c = 〇 group is the same as that of Example 1 in IR analysis. Example 1 2 ~ 1 4 (by IR Bismuth sheet > Confirmation of the hardening reactivity of 导 for optical waveguides) Use in the example !!! The obtained use is 3 fluoro (human fat composition) and the modulation is the same as that of Example 4 Operation of fluorine prepolymer (I) to modulate materials for optical waveguides

572906 V. Description of the invention (54) (composition for coating), it becomes the polymer concentration shown in Table 3, the type of active energy ray hardening initiator, and the active energy ray hardening starting dose. (2) Production of film for IR analysis The same procedure as in Example 7 was carried out. (3) The measurement of the hardening reaction rate by IR analysis is the same as in Example 7 ', and the hardening reaction rate at the time of irradiation with a light irradiation amount of 15 00 mj / cm2 is calculated. The results are shown in Table 3. Example 1 5 The material for an optical waveguide (the coating composition) modulated in Example 1 2

), And also add 20% by weight to the polymer as a hardener

CH2 = CF — C — 〇CH2C6F12CH2〇—C—CF = CH II 2 〇 It is used to manufacture materials for optical waveguides (fluorine-containing resin composition for coating) with a hardener. Using this resin composition, a film for R analysis was produced in the same manner as in Example 12 and the curing reaction rate was measured. The results are shown in Table 3.

2066-4683-PF (N); Tcshiau.ptd Page 59 572906_ V. Description of the invention (55) Table 3 Example 12 Example 13 Example 14 Comparative Example 15 Fluorin-hardening polymer Example 11 Example 11 Implementation Example 11 Example 11 _〇 (C = 〇) CF = CH2 group content (mol%) S4 S4 84 S4 solvent MEK MEK MEK MEK polymer concentration (wt%) β 8 δ 8 activation energy ray hardening initiator 2-Hydroxy-2 · methyl 2,2-dimethoxybenzyl alcohol 2-hydroxy-2-methylbenzene to polymer ratio (mm%) Phenylacetone 2.0 2-phenylethyl with benzene 2 -0 2.0 Acetone 2.0 Hardener — One — Ratio of polyfunctional acrylic acid U to polymer (accent: ¾) One to one 20 Hardening reaction rate (%) (1500m J / cm2B temple) 73.9 55.0 40.6 64.0 1) Multifunctional Propionic acid: CH2 = CF (C = 〇) 〇CH2— (CF2) 6—CH2〇 (C = 〇) CF = CH2 Synthesis Example 2 (Synthesis of Homopolymer of Fluorinated Allyl Ether with OH Group ) Except in Synthesis Example 1, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxonanol) 20. (^ and [H + CF2CF2 > yC〇〇tr 8.0 wt% perfluorohexane soluble 10. Other than Og, the rest is the same as in Synthesis Example 1. Synthesis was carried out. The obtained polymer was purified to obtain a colorless and transparent polymer 18.2 g. By 19F-NMR, NMR analysis, and IR analysis, When the polymer was analyzed, it was found that it was a fluoropolymer composed only of the structural units of the aforementioned fluorinated allyl ether and having a radical at the end of the side chain. In addition, tetrahydrofuran ( The number-average molecular weight measured by GPC analysis of THF) was 30,000, and the weight-average molecular weight was 59000. Synthesis Example 3 (Copolymer of fluorinated allyl ether and vinylidene fluoride having 0H group)

2066-4683-PF (N); Tcshiau.ptd Page 60 572906 V. Synthesis of the description of the invention (56)) In a high pressure steel made of stainless steel with a capacity of 300 ml, equipped with a valve, a pressure gauge and a thermometer, 'fill perfluoro- (119, 9-tetrahydro-2, 5_bistrifluoromethyl-1,3,6-dioxonanol) 34.2g, CH3CC12F (HCFC-141b) 20 0g, and di-n-propyl peroxycarbonate (NPP) The 50% by weight methanol solution 0.16g was cooled with dry ice / methanol solution, and was substituted into the system sufficiently with nitrogen. Next, 5.8 g of vinylidene fluoride (VdF) was charged through a valve, and at 40 ° C, vibration was performed and a reaction was performed. With the progress of the reaction, the calculated pressure in the system was reduced from 4.4 MPaG (4.5 kgf / cm2G) before the reaction to 0.98 MPaG (1.0 kgf / cm2G) after 12 hours. At this point in time, unreacted monomers are released, the precipitated solids are taken out and dissolved in acetone, and then reprecipitated by using a mixed solvent (50/50) of hexane and toluene to facilitate separation Out copolymer. 2 g。 Until the copolymer was made constant, vacuum drying was performed to obtain the copolymer 31.2 g. When the analysis was performed by NMR analysis and 19F-NMR analysis, it was found that the composition ratio of the copolymer was fluorinated allyl ether containing ¥ (^ / 〇H group is 55/45 moles. In addition, The number average molecular weight measured by GPC analysis using tetrahydrofuran (Thf) as a solvent was 1 2000, and the weight average molecular weight was 1 8000. Synthesis Example 4 (Synthesis of a fluorine-containing activation energy ray hardening initiator) A 200 ml four-necked flask equipped with a circulating cooler, a thermometer, a stirring device, and a dropping funnel was charged with 2.0 g of 2-hydroxy-2-methylphenylacetone,

2066-4683-PF (N); Tcshiau.ptd page 61 572906 V. Description of the invention (57) 20g of pyridine 1. Og and CF3CF2CHC1 / CC1F2CF2CHC1F mixture (HCFC-225), ice-cooled to below 5 ° C. Under nitrogen flow, while stirring, dripping within 1 hour

fc-c6f12 ~ cf 11 II 2.5 g. 〇Hours of stirring was continued after the end of the dripping. The ether solution after the reaction was placed in a separating funnel, washed with 2% hydrochloric acid water and 5% NaC 1 water, and the organic layer was separated and dried with magnesium sulfate, and then, The product 2.6 g was separated by distillation (yield: 62%). When the obtained product was investigated by NMR analysis, 19F-NMR analysis, and IR analysis, it was found that it was ch3 ch3 c-c-〇c-, cf2 ^ c〇-c O CH, ο -c II ch3.

Example 16 6 (Synthesis of hardening fluorine-containing prepolymer (J) having α-fluoropropenyl fluorenyl group) In a 200 ml four-necked flask equipped with a circulation cooler, a thermometer, a stirring device, and a dropping funnel, 40 ml of methyl ethyl ketone (MEK), 5.0 g of a fluoro-containing allylic ether-containing separate polymer obtained in Synthesis Example 2 and 2.0 g of pyridine were charged, and ice-cooled to 5 ° C or lower. While stirring under a nitrogen stream, 2 g of α-fluoroacrylic acid fluoride was dropped in about 30 minutes. After dripping, increase the temperature

2066-4683-PF (N); Tcshiau.ptd Page 62 572906 V. Description of the Invention (58) Until room temperature, stirring was continued for 4.0 hours. After the reaction, the MEK solution was put into a separating funnel, and the organic layer was separated by repeatedly washing with water, 2% hydrochloric acid, 5% NaC1, and water. Then, the organic layer was separated by sulfuric acid. Magnesic anhydride was dried to obtain a curable fluorine-containing prepolymer. The polymer concentration after filtration was 10.7 wt%. When the fluorine-containing prepolymer was investigated by 19F-NMR analysis, it was found that it was 10 CCF = fluorine-containing allyl ether containing a CH2 group. / Fluoroallylic allyl ether containing 0H group = 30/70 mole%. In addition, when the R analysis was performed in the same manner as in Example 1, it was observed that the absorption of the carbon-breaking double bond was 1,661 cnri, and the absorption of c = 0 group was 1,770 cm-1. Example 17 (Synthesis of sclerosing fluorine-containing prepolymer (I) having α-fluoropropenyl fluorenyl group) Except for using fluorinated allyl scale containing fluorenyl group and VdF obtained in Synthesis Example 3 Copolymer 5. ·, pyridine 1.1 g, and fluoroacrylic acid fluoride: the rest are the same as those in Example 16, and a synthetic hardenable fluorine-containing prepolymer I μ (valley solution). The polymer concentration was 9.9% by weight. When investigating by F-NMR-〇CCF = Including the right one ^ ^ ^ 2 Earth & Fluoropropyl propyl / containing 0H group implementation contact (become Λ \ ^ 5/85 Moore % Copolymer》) / Physical property evaluation of light-curing film for leather road members (1) Modulation of materials for optical waveguides was carried out in Example 16; 2: A. Yuzhi 3 fluorine prepolymer (MEK Add solution

) / 2906 V. Description of the invention (59) Enter the ship to adjust the polymer concentration to 50% by weight. When MEJ (,,,,,,,,,,,,-,-,,,-,,-,,-,,-,,-,,-,-,-,-,,-,,-,,-,,,,,,,,,,,,,,,,,,,,, A, 六, a fluorine-containing prepolymer, is added as an active energy ray to harden ..., the polymer becomes 2 turbid methylene dipropylene. Reduction by weight =: When the hardening energy ray hardness obtained by Example 曱 I is 3.6% by weight, basic acetone is added, and the polymer is used as a material for optical waveguides to form a colorless and transparent solution. (2 ) Use of light guides: Evaluation of light-hardened films with routing Λ materials is used in the description of the light guides that are mixed with the precursor M and the material for the wave path (the light guide of the hardening initiator prepared for coating is described in "(Π , The same as that in Example 4), and the evaluation was performed, and the hardening reaction when the light was irradiated with i500mj / cm2 cm2 light irradiation ° = Example 8, measured at 150mJ / H ^ 4ij ffl T) QP ^ y ", ... The results are shown in Table 4. In addition, an analysis was performed to confirm the physical properties of the light-hardened film of Example 19 (becoming a light-turbid turbid field). (1) For optical waveguides The material was prepared by focusing on the gas-containing prepolymer (MEK solution) obtained in Example 17 and adding MEK to adjust the polymer concentration. It becomes 8% by weight. It is also added to the initial ΐ: 2: JH body armor ::: When added as active energy ray hardening%, it is compatible with each other and becomes a diketone :: The polymer becomes a U weight wave path material. In addition, 2; J's liquid in February. This was analyzed by DSC as a light guide, and confirmed as page 642066-4683-PF (N); Tcshiau.ptd 572906 5. Description of the invention (60 ) Non-crystalline. (2) Evaluation of light-curing film of material for optical waveguides Using the obtained material for optical waveguides (composition for coating), the same evaluation as in Example 18 was performed. The results are shown in Table 4 Table 4 Example is Yin Example 19 Prepolymer Example 16 Example 17-〇 (c = 〇) cf = ch2 group containing child S9 35 fluorine content rate (*) 56 57 activated energy ray hardening initiator Ratio of fluorinated initiator 2-mercapto-2-methylphenylacetone to polymer in Synthesis Example 4 to polymer (reunion) 3.6 6.7 UV irradiation (mJ / cm2) 1500 1500 Hardening reaction rate 88.7 75.7 Refractive index hardening Before 1.368 1.369 After hardening 1.375 1.377 Absorbance coefficient (cnrri) 1310nm 0.026 0.051 1550nm 0.22 0.28 Solvent resistance 〇〇heat resistance 〇 Synthesis Example 5 (Synthesis of oligomers containing 0H group fluorine-containing allyl ether) In a 100 ml glass four-necked flask equipped with a stirring device and a thermometer, perfluoro was placed -(1,1,9,9 -tetrahydro-2, 5 -bistrifluorofluorenyl-3, 6 -dioxonyl alcohol)

2066-4683-PF (N); Tcshiau.ptd page 65 572906 V. Description of the invention (61)

CH2-CFCF2OCFCF2〇CFCH2OH

II cf3 cf3 (hereinafter referred to as "fluorine-containing allyl ether a") 5.2g and ch2 = cfcf2〇cfcf2〇cfh cf3 cf3 (hereinafter referred to as "fluorine-containing allyl ether β") 1 4.2 g, After the nitrogen substitution was sufficiently performed, and then stirred for 24 hours under a nitrogen flow at 20 t, a highly viscous solid was formed. The solid obtained by dissolving in diethyl ether was poured into all 1 hexane, followed by separation and vacuum drying to obtain 12 · 2 g of a colorless and transparent polymer. … When the polymer was analyzed by NMR, 1H-NMR analysis, and IR analysis, it was found that the polymer was composed of the aforementioned two types of fluorine-containing allyl ether structural units and had a hydroxyl group at the end of the side chain. polymer. In addition, the weight average molecular weight (Mw) determined by GPC analysis using tetrahydrofuran (THF) in the solvent was 2 1 0000, and the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mη) (Mw / Μη) is 1.3. The 5% by weight decomposition temperature measured by the following method was 360 ° C. (Measurement of 5% by weight decomposition temperature) Heating was performed by using TG / DTA (TG / DTA220 manufactured by Seiko Instruments Inc.) under conditions of 200 ml / minute dry air and 10 ° C / minute heating rate. The temperature at which 5% by weight was thermally decomposed (weight reduced) was taken as the 5% by weight decomposition temperature.

2066.4683-PF (N); Tcshiau.ptd Page 66 572906 V. Description of the Invention (62) Synthesis Example 6 (Synthesis of Homopolymers and Polymers Containing Fluorinated Allyl Bonds with 0H Group) Except for the Synthesis Examples 5 'The amount of the two types of fluorinated allyl ethers a and 8 is used in addition to the amounts shown in Table 5, and the rest is the same as in Synthesis Example 5. Polymerization was performed to obtain the two types of fluorinated allyl groups A fluoropolymer composed of scale structural units and having a hydroxyl group at a side chain terminal (Synthesis Examples 6, 7 and 9) and a fluoro-containing diisopropyl alone polymer (Synthesis Example 8). The physical properties of these polymers are shown in Table 5. ° Table 5 — 5 6 7 δ 9 A (g) b (g) 5.2 14.2 10.3 9.5 15.3 4.8 30.2 0 72.1 S_3 Polymer formation child (g) 12.2 13.1 13.1 19.6 50.2 Polymer physical properties Mw ( χ1〇4) Mw / Mn collar decomposition temperature Ί 2.1 1.3 360 2.2 1.5 364 2.7 1.5 364 3.0 1.7 381 1.9 1.5 370 Examples of solid yoke 20 to 24 (hardened fluorine-containing prepolymer with α-fluoropropenyl group (I Synthesis of) Λ

In addition to using the fluorine-containing allyl ether polymers containing fluorenyl groups obtained in Synthesis Examples 5 to 9 shown in Table 6, the amount shown in Table 6 was used instead of the synthesis example in Example 1. The obtained fluorine-containing compound containing OH group was similarly formed into a hardening fluorine-containing prepolymer having an α-fluoropropenyl group except for the reaction conditions shown in Table 6.

572906 V. Description of the invention (63) Based on the obtained hardened fluorinated prepolymer, lgF_NMR analysis was conducted to investigate the results of fluorinated dialkyl ether A and fluorinated allyl ether B containing 0H groups. When the content (mole%) of the resulting structural unit is as shown in Table 6. When IR analysis was performed on a person coated on a NaC 1 plate and becoming a cast film at room temperature, it was observed that the absorption of the carbon-carbon double bond was 1661cnfl, and the absorption of the c = 〇 group was 1 770 cm-1.

Examples 25 to 29 (becoming a light guide, Nita Erji-evaluation) Light-curing film of a waveguide member

In addition to using the + + human & 24 manufacturers separately in Table 7 and di 'fluorine prepolymer f (in addition to the fluorinated prepolymer of the benzofluorenyl group in Example 2) The α-fluorine film was hardened and thinned; the rest was the same as in Example 4 except that it was made by DSC. The results are shown in Table 3. This is the analysis for the sake of confirmation. crystallization

2066-4683-PF (N); Tcshiau.ptd Page 68 572906 V. Description of the invention (64). Table 7 Example 25 Example 26 Example 27 Example 2S Example 29 Prepolymer Example 20 Example 21 Example 22 Example 22 Example 23 Example 24 (C = 0) CF = CH2 Base-containing child (Moore 35) 27 53 78 100 δδ Fluorine content (Chonghuan) 62 59 57 55 50 Active energy ray hardening initiator 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methyl Phenylacetone 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methylphenylacetone 2-hydroxy-2-methylphenylacetone to polymer ratio (wt%) 2.0 2.0 2.0 2.0 2.0 UV Irradiated child (mJ / cm2) 1800 1800 1800 1S00 1800 Time-lapse rate before hardening 1.32 1.352 1.354 1.361 1.364 1.369 1.371 L381 1.368 1.375 Solvent resistance 0.000 Heat resistance 0.000 Example 30 (Become a light guide Evaluation of the physical properties of the light-curing film of the member for the wave path) (1) Preparation of the material for the light guide wave path The hardening fluorine-containing prepolymer obtained in Example 24 was dissolved in propylene glycol monofluorenyl ether acetate (PGMEA) ), A solution having a prepolymer concentration of 40% by weight was prepared. To 10 g of the PGMEA solution of the fluorine-containing prepolymer was added as an activation energy ray hardening initiator (photo radical initiator) and obtained in Synthesis Example 4.

2066-4683-PF (N); Tcshiau.ptd p. 69 572906

5 g of a 1% by weight iMEK solution of the compound was used to prepare an optical waveguide material for coating. (2) Manufacture of a light-hardened film for a material for optical waveguides On a 5 inch silicon wafer, the material for optical waveguides (coating composition) was applied in a rotating manner to obtain a film thickness of 1 〇 " m Hardened film. After the film was dried, a high-pressure mercury lamp was used to irradiate ultraviolet rays at an intensity of 800 m / cm2U at room temperature to produce a photocurable film. (3) Evaluation of the light-curing film of the material for optical waveguides For the cured film obtained, the near-infrared region (130 nm and 1 550 nm) was measured using Prismcoupler (model 2010, trade name) made by the company. At the middle refractive index, the refractive index was 1.373 at 1300 nm and 1.371 at 1550 nm. Example 3 1 (Physical property evaluation of a light-hardened film to be a member for a light guide wave path (1) Modulation of a material for a light guide wave path The material for coating obtained in (1) of Example 30 was used. Case (2) Light guide The manufacture of the light-hardening film of the material for the wave path makes the predetermined amount of the material for the light-guide wave path (the composition for coating) flow into a concave mold of 15 mm X 15 mm X 1 mm to obtain three types of hardened casting thin films with different film thicknesses. After drying these films, use a high-pressure mercury lamp to irradiate ultraviolet rays at room temperature at an intensity of 1 800mJ / cm2u to produce light-hardening films with different film thicknesses (film rabbits ~, 朕 thickness 280 / zm, 450 / zm and 1 020 " m) 〇

2066-4683-PF (N); Tcshiau.ptd Page 70 572906 V. Description of the invention (66) (3) Evaluation of the light-hardened film of the material for optical waveguides uses a weak absorption measuring device (manufactured by JASCO Corporation) MAC-1 / trade name) in a range of measurement wavelengths from 900 to 1700 nm. In the inner region, the absorption intensity of the photocurable film was measured at 1 nm (measurement temperature: 24 C). In addition, even for thin films having different thicknesses, the absorption strength was measured in the same manner. The film thickness was normalized, and the effect of dereflecting the surface was examined, and the absorption loss of the material itself was investigated. The results are shown in Figure 3. As can be clearly seen from Fig. 3, it was found that the absorption losses at 1 and 1 were 0.1 dB / cm & 0.5 dB / cm, respectively. In the near-infrared region, it showed extremely good transparency. Embodiment 32 (Manufacture of optical waveguide type element) The formation of the optical waveguide in the optical waveguide type element is performed in the following order. As the material for 4 parts', the material for the optical waveguides modulated in Example 16 was used as the material for the cladding portion, and the optical waveguide was manufactured using the fluorine-containing prepolymer prepared in Example ^. Each of these two materials' is dissolved in a methyl isobutyl mesh to become a solvent. 2 First, a layer 0 material is coated on a plastic substrate, a silicon substrate, or the like. After the above-mentioned drying and drying treatment is performed, a material for the core portion of about 8 ϋ is coated on the film of the material for the cladding portion. Then, light is irradiated through the photomask to harden the film. Then, the non-hardened α trowel for washing the core in a flowing manner with a solvent was processed into a linear rectangular pattern with a length of 50_, a width of 8 #, and a height of 8 ”as the core. After, according to Figure 2

572906 V. Description of Invention (67) The cladding portion will be described. Therefore, the cladding portion is coated on the core portion to manufacture an optical waveguide. Next, for the measurement of the propagation loss of the manufactured optical waveguide, the propagation loss is measured by passing a light having a wavelength of 130 nm in the core. As a result, it was 0.5 dB / cm. In addition, in the environment of temperature 80 ° C and humidity 85% RH, the optical waveguide manufactured here was stored for 1 week, but the propagation loss was not changed at all. 'Industrial Applicability' According to the present invention, a material for an optical waveguide which is transparent and can be hardened by light at the same time. In addition, the use of members for light-guiding waveguides can facilitate the use of near-infrared-transparency light-guiding waveguides, which can provide a hardened material that maintains near-infrared rays and realizes heat resistance and high-elasticity waveguides for polymers. -A road-type device with improved heat resistance and low water absorption.

572906 Brief description of drawings _ Figure 1 is a schematic cross-sectional view of the I% HI 0 / X guided wave path type element of the present invention. Fig. 2 (d) is an operation diagram for explaining the manufacturing operation of the optical waveguide type element of the present invention. Fig. 3 is a graph showing absorption loss at each wavelength of the light-hardened film produced in Example 31. [Description of symbols] 1: substrate 3: film 5: cladding portion 7: active energy ray

No. 73

Claims (1)

5729〇6 _ Case broken 91103639 Amendment: Shen Fanyu-卞 Plant II ^ Fluorine-containing optical waveguides (I) material for optical waveguides, pot; = containing J prepolymer; ⑴ system is uu content rate 25 Weight; knot ^^ :: Paleo and '(2) has a carbon-carbon double bond in the polymer side chain and / or polymer, and the fluorine-containing prepolymer (I) at the end of the bond is of the chemical formula ( 1): —fM 今 —— (1) [In the chemical formula, the structural unit M is a chemical formula (μ -irCX ^ X9 —CX3 ^ XCX4X5) v- ^ C = 〇) b (〇) —R f (M) ( In the chemical formula, X1 and X2 are the same or different to form H or F; X3 is HF, CH3 or CF3; X4 and X5 are the same or different to form Η, F or (: (? 3; Rf: in carbon number 1) Fluorine-containing alkyl group of ~ 40 or fluorinated alkyl group having a strong 3 bond of 2 to 100 carbon atoms and 1 to 3 of Y1 (Y1 has an ethyl group name at the end # δ 土 七七 ~ carbon Substituting a bond and a monovalent organic group having a carbon number of 2 to 10); a is an integer of 0 to 3; b and c are the same or different and become 0 or 1) due to the person & ^ ^^ 4 The structural unit and early structure A caused by the early body B are due to The structural unit caused by the fluorine-containing ethylenic monomer and copolymerizable monomer at the position M includes 0.1 to 100 mol❾ /. The structural unit M and 0 to 99 qmiaotian, so ^ · a旲 _% of the number of structural units A of the gas-containing aggregates with an average molecular weight of 50 0 to 1 0 0 0 0 0. 2 · For the fluorine-containing optical waveguide material for the first item of the scope of patent application, which 2066-4683-PFl (N) .ptc Page 74 572906 The fluorine content of the fluorine-containing prepolymer (i) is 40 dwt. 3, such as the fluorine-containing optical waveguide in item i of the patent application scope. In the above, the fluorine-containing prepolymer (I) is a polymer having a maximum absorbance coefficient of 1250 to 1320 nm and a skin material of the following material. '4 in the long range, such as in the fluorinated optical waveguide for item 1 of the scope of the patent application' Fluorine-containing prepolymer (I) is a wave at 1530 to 1570 nm ', and the maximum absorbance coefficient is 1 cm- i or less polymer. 5 in the dry circle. For the fluorine-containing optical waveguide for item 丨 of the patent application range, the fluorine-containing prepolymer (I) is at the end of the side chain, and the right # :, its bond. A slave-carbon double middle 6. If the material for fluorine-containing optical waveguides in the scope of patent application No. 1 is applied, the carbon-carbon double bond system is a radically reactive ethylene-carbon double carbon bell, 7. Fluorine-containing optical waveguide material for the scope of the patent No. 丨, bond < carbon-carbon double bond system with cationically reactive vinylic carbon 鍅 8., 8. Fluorine-containing optical waveguide material for the scope of the patent application No. 丨, Containing fluorinated prefluoride (I), a fluoropolymer of the chemical formula (!)., The structural unit M is a chemical formula (Ml CX3) ~ [(CX4Xs > T ~ 4〇 > T_ ^ f (M)) ( In the chemical formula, X1 and X2 are the same or different to become H or ρ; χ3 is η, F, CH3 or CFS; X4 and X5 are the same or different to become H, F or Cf3; Rf is in the inverse number of 1 ~ 40 of 3 fluorinated radicals or fluorinated alkyl radicals with 2 to iqq carbon bonds and 1 to 3 fluorescein 1 (γι has an ethylenic carbon-carbon double bond at the end 2066-4683-PFl (N) .ptc Page 75 572906 ___Case No. 91103639 ___ Year. Month Date _ Amendment __ VI. Organic group applying for patent range bond and monovalent organic group with 2 to 10 carbon number) ; A is an integer of 0 to 3, and c is a structural unit M1 shown by 0 or 1) due to the fluorine-containing ethylenic monomer. 9 · The material for fluorine-containing optical waveguides according to item 1 of the scope of patent application, wherein the 'fluorine-containing prepolymer (I) is a fluorine-containing polymer of chemical formula (1); the structural unit M is a chemical formula (M 2): ( M2) (In the chemical formula, Rf is a fluorinated alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having an ether bond with 2 to 100 carbon atoms, and 1 to 3 of which are bonded to γ1 (γι is at the end The structural unit M due to a fluorine-containing ethylenic monomer as shown in an organic group) having an ethylenic carbon-carbon double bond and a carbon number of 2 to 10). 10. If the gas-containing prepolymer (" in the fluorine-containing optical waveguide of item 丨 in the scope of the patent application) is the material of the chemical formula (1), the structural unit M is the chemical formula (M3): 1. 物 'CF -CF I 〇 — R f. (M3) (In the chemical formula, Rf is a gas-containing alkyl group having an ether bond of 2 to 100 carbon atoms with a carbon number of 1 to 4 and a combination of 3 to γι. Ethylene carbon-carbon double bond with a carbon number of 2 ~ 10. The price is shown as', machine base). Soil made by gas-containing ethylenic monomer. Π As in the scope of patent application 1A8_ any-item Early :: 3 Light 2066-4683-PFl (N) .ptc Page 76 572906 VI. Patent application scope Guide material 'wherein' of Y1 of Rf in the aforementioned chemical formulas (M), (ΜΙ), (M2) and (M3) At least one is bound to the terminus of Rf. Fan Li specially requested to apply the formula as described above, and the material in J 1 Y} was used in the 3 ^ Μ C C wave and the guide} light g fluorine C containing, item 1 — 0 C ~ 〇) — Υ 2 (In the chemical formula, Υ 2 is an alkenyl or fluorinated alkenyl group having 2 or 5 carbon atoms with an ethylenic carbon-carbon double bond at the terminal; the same or different and becomes 0 or 1). (Before applying the formula, please use the material of 5 1}) Use M3 channel C wave and guide 3 light g fluorine C containing, the term Π -〇 (C = 0) CX6-GX7X8 (In the chemical formula, X6 is Η, F, CH3, or CF3; Γ and x8 are the same or different to become Η or F.) ▲ 1 4 · A fluorine-containing optical waveguide material, which is characterized by the following features: In addition to the fluorine-containing prepolymer (I) described in item 1, an active energy ray hardening initiator (Π) is added to form a fluorine-containing optical waveguide material 15 · The fluorine-containing optical waveguide material 2 according to item 14 of the scope of patent application, wherein the active energy ray hardening initiator (Π) is a light radical generation 3 (Π -1). Χ 572906 _η Case No. 911036 plus 6. Scope of patent application 1 6. If the scope of patent application is included! Item 4 contains the activation energy ray hardening initiator (: road material 枓, 2).打打 尤 'generator (Π ~ 17 · —A kind of fluorine-containing optical waveguide component, the fluorine-containing component described in the U.S. patent application is composed of hardened hardened material. It is composed of special materials-specific H-around H A component for a gas-optic guided wave path is characterized in that, in addition to Shin: Yu composition · (including active energy ray hard dagger: Bu), it is also composed of a hardened material composed of modified materials to contain gas: = Among them, fluorine-containing prepolymerization The body ('Shen ^ Zhizhi contains ^ members for the light guide wave path, including prepolymers, activation energy after shooting = = the biological agent described in item 6 of Li Siwei (π_ " Π) is a photo-radical emission. 20. In the scope of the patent application, the fluorine-containing prepolymer is activated by a β / random guided wave path member, the fluorine-containing prepolymer, and is activated. Π-2) 〇1 hardening initiator ⑴ series photoacid generator 2 1-a kind of fluorine-containing optical waveguide 苴 # r, ® ^ 17, M „^ ^ t tf i The maximum value of the number of times Λ, The range is below w. 5 fluorine optical waveguide components, special features / recognition of the 17th patent scope, especially in the application. # 声 在 bismuth ° 1 530 ~ 1 5 70nm 诸 旦 # of the hardened material that has been loaded, and the maximum value of the coefficient of precedence is less than one. Wavelength range 2066-4683-PFl (N) .ptc page 78 572906 Amendment No. 91103639 ^ p | Sixth, the scope of patent application = · A type of optical waveguide-type element 'is composed of an anger part and a cladding part 2 guided-wave path type element', characterized by ☆: at least the core and the cladding part Structure: For the gas-guided optical waveguides described in item 17 of the scope of patent application 24. For optical waveguide-type components in the scope of patent application 23, use directly: ί Department is listed in item 17 of the scope of patent application It is composed of a component for a fluorinated light guide wave path. $ 久 格 25. If the light guide wave path type element of the scope of patent application No. 23 or 24, wave: use; :::: The gas-containing light guide described in the scope of patent application No. 17 2 6 · —A component for a fluorinated optical waveguide, characterized by being hardened: a hardened material of the fluorinated optical waveguide as described in item 1 of the patent scope. Wind 2J · A component for a fluorinated optical waveguide , Which is characterized by: The maximum value of the absorbance coefficient within the range of 29 to 132% of the material is lcnrl or less. Qianwei 2 8. —A kind of fluorine-containing optical waveguide component, characterized by the hardening described in Item 26 of the Nellie range. The maximum value of the absorbance coefficient in the wavelength range of 1 530 ~ 1 570nm is 1 cm-1 or less. Xi Zhi 2 broadcast 9 ·, Γ optical-guide-type element 'is composed of the core and cladding Structure 1. The road-type element is characterized in that at least j 'of the core portion and the cladding portion is constituted by a member for an optical waveguide containing I described in the item of the scope of patent application. 30. If the optical waveguide device of item 29 of the patent application scope, 572906